WO2017005078A1 - Ternary material coated with three-dimensional network structure of coupled carbon nanotube-graphene composite and manufacturing method thereof - Google Patents

Ternary material coated with three-dimensional network structure of coupled carbon nanotube-graphene composite and manufacturing method thereof Download PDF

Info

Publication number
WO2017005078A1
WO2017005078A1 PCT/CN2016/085323 CN2016085323W WO2017005078A1 WO 2017005078 A1 WO2017005078 A1 WO 2017005078A1 CN 2016085323 W CN2016085323 W CN 2016085323W WO 2017005078 A1 WO2017005078 A1 WO 2017005078A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
ternary material
carbon nanotube
nickel
carbon nanotubes
Prior art date
Application number
PCT/CN2016/085323
Other languages
French (fr)
Chinese (zh)
Inventor
王文阁
宋春华
王瑛
乔文灿
赵成龙
冯涛
张智辉
赵艳丽
Original Assignee
山东玉皇新能源科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 山东玉皇新能源科技有限公司 filed Critical 山东玉皇新能源科技有限公司
Publication of WO2017005078A1 publication Critical patent/WO2017005078A1/en

Links

Images

Classifications

    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 battery materials, in particular to a ternary material coated with a coupled carbon nanotube-graphene composite three-dimensional network structure and a preparation method thereof.
  • Lithium-ion batteries with high energy density, small volume and long cycle life have been widely used.
  • key performance indicators are high energy density and fast discharge capability.
  • countries such as the United States and Japan have an energy density requirement of 300 Wh/kg for the next-generation lithium-ion power battery, which is more than twice the energy density of the LiFePO 4 power battery currently under development. Therefore, the ways to improve the energy density of the lithium ion battery are mainly: first, to increase the specific capacity of the positive electrode material; second, to increase the electrode potential of the positive electrode material to improve the operating voltage of the battery.
  • the cathode materials LiCoO 2 , LiMn 2 O 4 and LiFePO 4 which have been commercialized at present have the actual specific capacity of only 145 mAh/g, and have the disadvantages of high cost, poor safety and poor consistency.
  • the nickel-cobalt-manganese composite material has a high capacity, the actual specific capacity can reach 200 mAh/g and has the advantages of low cost, good stability and high safety.
  • some lithium cobalt oxide has been gradually replaced.
  • Co can effectively reduce the cation mixing, stabilize the layered structure of the material, Ni can increase the capacity of the material, Mn can not only reduce the cost of the material, but also improve the safety and stability of the material. As a result, the material demonstrates excellent cycle performance and is recognized by the market.
  • lithium nickel cobalt manganese ternary materials Since its research in 2001, lithium nickel cobalt manganese ternary materials have been rapidly industrialized due to their stable specific capacity, good safety and structural stability, and moderate cost, especially when the price of cobalt is high. Its cost advantage is more obvious.
  • ternary materials are mainly used in cylindrical and square lithium ion batteries of steel or aluminum.
  • lithium nickel cobalt manganese ternary materials are mostly used in mobile power, functional mobile phones and electric bicycles where energy density is not critical.
  • Lithium Cobaltate is mainly used, mainly because of the shortcomings of low density, easy to expand, etc. in ternary materials, and its application in power lithium-ion batteries and high-voltage system lithium batteries. It is still in the research and development stage.
  • lithium nickel cobalt manganese oxide material is the mainstream of R&D and industrialization, and it is also the cathode material with high potential and high energy density small lithium ion battery for the next generation of power lithium-ion batteries and electronic products.
  • the high-density and high-voltage nickel-cobalt-manganese ternary materials have lower requirements on environment and equipment, are less difficult to prepare and process, have high consistency and reliability, and can achieve high energy density targets.
  • the material After long-term research, although the material has good electrochemical performance, in terms of practicality, there are still problems to be solved.
  • the ternary material After the ternary material is delithized in the first week, it is easy to cause oxygen loss and phase change, resulting in a large first week irreversible loss.
  • the material has low electrical conductivity and poor macro-rate performance.
  • the ternary material is easily cation-discharged in the lithium layer, and the organic electrolyte and the electrode material are easily reacted strongly in a wide discharge voltage range, thereby increasing the impedance of the battery during charging and discharging, and reducing the electrochemical of the material. performance.
  • the preparation method of the material includes a high temperature solid phase method, a coprecipitation method, a sol gel method, a hydrothermal method, a spray drying method, a controlled crystal precipitation method, and the like, and further, the structure of the ternary material can be made more stable by appropriate doping.
  • the ion mixing effect is reduced, and the cycle performance of the material can be effectively improved.
  • the doped element should enter the position where the ion is to be replaced.
  • the radius of the doping ion and the ion to be replaced should have similar radii to ensure the stability of the material structure.
  • the doped ions themselves must have good stability.
  • the electrolyte reacts and no redox reaction occurs.
  • Doping is divided into anion doping and cation doping.
  • the doping elements of the cation are Ti, Mg, Al, Cr, Zr and rare earth elements, etc., the anion doping is mostly a halogen element, and the doping is more F - ion.
  • surface coating of ternary materials is also a hot topic in current research. It refers to coating a film material on the surface of the material. The film material generally does not change the structure of the material itself, and the coating can improve the conductivity of the material. Rate, reduce the erosion of the material by the electrolyte, thereby improving the cycle performance and rate performance of the material.
  • the means for surface coating include oxide coating, phosphate coating, fluoride coating, lithium ion battery cathode material coating, and carbon coating.
  • the key carbon coating Guo R et al. successfully synthesized carbon-coated nickel-cobalt-manganese ternary materials using PVA with low cracking temperature, and optimized its carbon content. When the carbon content is 1.0wt%, the material The cycle performance and rate performance are greatly improved compared to uncoated materials.
  • Sinha NN et al. synthesized a carbon-coated submicron-sized nickel-cobalt-manganese ternary material precursor using a one-step method and using glucose as a carbon source.
  • the nickel-cobalt-manganese hydride crystal was obtained by synthesizing at 900 ° C for 6 h.
  • the carbon coating on the surface of the study has excellent cycle performance and greatly suppresses the capacity decay at high rate discharge.
  • Rao et al. prepared LiCo 1/3 Ni 1/3 Mn 1/3 O 2 by microemulsion method, and then prepared LiCo 1/3 Ni 1/3 Mn 1/3 O 2 graphene composite by ball milling.
  • the specific discharge capacity at the first week of 1C and 5C charge and discharge was 172 mAh/g and 153 mAh/g, respectively, and the performance of the material was improved.
  • the graphene and the ternary materials were combined by ball milling. When the 3C was charged and discharged, the capacity retention rate was 82% after 20 weeks of circulation.
  • the present invention provides a coupled carbon nanotube-graphene composite three-dimensional network structure package for improving the lithium ion diffusion coefficient and electronic conductivity of a material and suppressing the capacity attenuation of a material at a high rate discharge. Covered ternary materials and preparation methods thereof.
  • the silane coupling agent is used to connect the graphene and the carbon nanotubes by a liquid phase self-combination method to form a three-dimensional network structure, and then the coupled carbon nanotube-graphene composite material and the nickel cobalt manganese ternary material are formed. After being uniformly dispersed by a physical method, it is coated on the surface of the nickel-cobalt-manganese ternary material, and is sintered in an inert atmosphere to obtain a uniformly coated product.
  • the invention overcomes the problems of low conductivity and small lithium ion diffusion coefficient and poor battery charge and discharge performance in the existing nickel-cobalt-manganese ternary material, and adopts the technical scheme that the graphene has strong electronic conductivity and reduces the electrode.
  • the interface resistance between the active material and the electrolyte is favorable for the conduction of Li + ;
  • the two-dimensional structure of the graphene sheet is coated on the surface of the electrode material, inhibiting the dissolution and phase transformation of the metal oxide, and maintaining the charge and discharge process.
  • the structure of the electrode material is stable.
  • One-dimensional carbon nanotubes provide excellent transport channels for lithium ion and electron conduction, and have high electrical conductivity.
  • this project uses a silane coupling agent to combine the two carbons into a three-dimensional network structure to coat the ternary material, utilizing the small size effect and surface unique to the composite carbon.
  • the effect controls the ternary material particles at the nanometer scale, and can increase the contact between the active materials, improve the conductance of the overall electrode, and facilitate the rapid storage and transport of lithium ions and electrons in the material. Reduce the polarization process and improve cycle performance.
  • the preparation method of the ternary material according to the present invention comprises the following steps:
  • the graphene has a specific surface area of 500-1000 m 2 /g, and the number of nanosheet layers is 2-6 layers, and the conductivity thereof is good; the specific surface area of the carbon nanotubes is 40-70 m 2 /g, and the particle diameter thereof is 60-100nm, its conductivity is higher; the mass ratio of graphene to carbon nanotubes is 1:1-5.
  • the weight ratio of graphene is 0.1-0.5%, and the weight ratio of carbon nanotubes is 0.2-0.5%.
  • the organic solvent is one or both of ethanol, isopropanol, n-butanol, glycerin, methanol, N-methylpyrrolidone and acetone.
  • the physical mixing mode is one or more of stirring, ultrasonication, and high-speed shear emulsification.
  • the protective atmosphere is a nitrogen atmosphere or an argon atmosphere.
  • the present invention obtains a graphene-carbon nanotube composite carbon material having a three-dimensional network structure by a liquid phase self-assembly method, and coats the surface of the nickel-cobalt-manganese ternary material.
  • the addition of the conductive agent graphene-carbon nanotube composite material reduces the interface resistance between the electrode active material and the electrolyte, facilitates the conduction of Li + , improves the conductivity of the material and the lithium ion diffusion coefficient;
  • the three-dimensional network structure of graphene-carbon nanotubes uniformly coats the surface of the ternary material, can inhibit the self-agglomeration of the material, and can increase the contact between the active materials, thereby ensuring the smooth passage of the electron ions in the circulation process. Improve the conductance of the whole electrode, reduce the polarization process during battery charging and discharging, and improve the cycle performance of the battery.
  • the composite of 0.4% graphene-carbon nanotube composite carbon material has a discharge capacity of 172.5 mAh/g in the first week at a rate of 0.2 C, and a discharge capacity of 158.2 mAh/g in the first week at a rate of 15 C, which is about 15 mAh/g higher than the raw material. After 110 weeks, the capacity retention rate reached 87.2%, and the capacity was still as high as 129.5 mAh/g under the 8C rate cycle, which improved the cycle stability and rate performance of the material.
  • the addition of carbon nanotubes reduces the production cost, and the new material has great theoretical guiding significance and engineering application value in the field of battery energy storage and power tram.
  • the method is simple in process, convenient in operation and easy to scale production.
  • the invention belongs to the field of electrochemical cells, and the product has a high discharge specific capacity and a long cycle life, and the preparation process is simple and easy to scale production.
  • 1 is a graph showing the rate performance of a composite ternary material prepared by combining different coating amounts of graphene-carbon nanotubes
  • FIG. 2 is a graph showing the rate performance of a composite ternary material prepared by combining graphene-carbon nanotubes in different proportions
  • 3 is a comparison diagram of rate discharge of materials and raw materials of composite graphene-carbon nanotubes and pure graphene;
  • Figure 5 is a scanning electron micrograph of the material after composite graphene-carbon nanotubes
  • Fig. 6 is an XRD chart of a graphene-carbon nanotube composite ternary material and a raw material.
  • the coupled graphene-carbon nanotube dispersion liquid is obtained;
  • 1.0 g of polyvinylpyrrolidone is dissolved in 50.0 g of deionized water at normal temperature, and after physical mixing and dispersion, 50.0 g of nickel-cobalt-manganese ternary material is added and stirred for 40 minutes.
  • the electrochemical performance of the cathode material of lithium battery was tested by constant current charge and discharge using Wuhan Landian CT2001A charge and discharge instrument.
  • the test cell was carried out in an argon-filled glove box using an electrolyte of LiPF 6 /EC+DMC+EMC (volume ratio 1:1:1), a separator of Celgard 2400 type diaphragm, and a counter electrode of metallic lithium sheet.
  • the electrochemical performance of the material was investigated using a CR2032 coin cell battery.
  • PVDF was dissolved in NMP to prepare a PVDF solution with a mass fraction of 4%, stirred well and placed in an oven at 80 ° C for 12 h for use.
  • the product obtained by coating in Example 1 and the nickel-cobalt-manganese raw material used, the conductive carbon black Super P, the conductive carbon black KS and the above PVDF solution were respectively mixed at a mass ratio of 88:3:3:6, and after sufficiently stirring, The slurry was uniformly coated on an aluminum foil, vacuum dried at 120 ° C for 12 hours, and then compacted by a two-roll tablet press.
  • the electrode piece with a diameter of 10 mm was made by a punching machine, and then the electrode piece was weighed, vacuum dried at 120 ° C for 5 hours, placed in a glove box, assembled into a CR2032 type button battery, and the button type battery was placed for 8 hours, and then subjected to a charge and discharge test.
  • Cyclic performance curve The battery was subjected to constant current charge and discharge test at a voltage range of 3.0-4.3 V (Vs Li + /Li) at 25 ⁇ 1 °C.
  • the Gs-CNTs(11)@LNCM curve in Fig. 4 is the cycle life diagram of the composite graphene-carbon nanotube material of Example 1 at 1C rate, and the material is subjected to the constant current charge and discharge at 0.2C for the first two weeks.
  • Activation treatment The first discharge specific capacity of the product of Example 1 was 172.5 mAh/g at a charge and discharge rate of 0.2 C, and the first discharge specific capacity of the raw material was 168.5 mAh/g.
  • Example 1 Under the charge and discharge of 0.2C, the first discharge specific difference is only 4mAh/g, and the effect is not obvious.
  • the product of Example 1 had a first discharge specific capacity of 158.2 mAh/g at 1 C rate charge and discharge, and the capacity retention rate was 87.2% after 100 cycles.
  • the first discharge specific capacity of the raw material was 142 mAh/g, and after 100 cycles, the capacity retention rate was 81.5%. That is, at the time of 1 C charge and discharge, the discharge specific capacity of the material prepared in Example 1 was higher than the discharge specific capacity of the raw material by 22 mAh/g after 100 cycles.
  • the lithium ion activity of the positive electrode portion of the product of Example 1 is higher after coating, and the insertion and extraction of lithium ions is easier with respect to the raw material. It can be seen that the modification of the nickel-cobalt-manganese cathode material by using graphene-carbon nanotubes reduces the polarization process inside the battery and improves the cycle stability of the material.
  • Rate performance curve The battery is subjected to constant current charge and discharge test in the range of 3.0-4.3V (Vs Li+/Li).
  • the Gs-CNTs(11)@LNCM curve in Fig. 3 is a graph showing the rate performance of the material after the composite graphene-carbon nanotube of Example 1.
  • the discharge specific capacities of the two groups are relatively close, which are 165.5 and 161.2 mAh/g, respectively.
  • the difference between the two groups is obvious, and the discharge of the material after the composite is obvious.
  • the specific capacity is 149.9 and 129.5 mAh/g, and the discharge specific capacity of the material can still reach 99.4 mAh/g when the current is discharged at 8C.
  • the discharge specific capacity of the material is only 96.3 mAh/g and 52.1 mAh/g when discharged at 5C and 8C, respectively, indicating that the high rate discharge performance of the composite graphene material is obvious. Improve and enhance the anti-attenuation ability of nickel-cobalt-manganese ternary materials.
  • the XRD pattern of the material is shown in Fig. 6.
  • the ratio of the intensity of the (003) peak to the (104) peak I (003) / I (104) is 1.199, 1.241, respectively. This ratio is often used to measure nickel.
  • the difference between this embodiment and the first embodiment is the graphene-carbon nanotube composite selected in the first step.
  • the ratio of materials is as follows:
  • Example 1 The difference between this embodiment and Example 1 is the ratio of the graphene-carbon nanotube composite material selected in the first step.
  • the specific preparation method is as follows:
  • Example 1 The difference between this embodiment and Example 1 is the ratio of the graphene-carbon nanotube composite material selected in the first step.
  • the specific preparation method is as follows:
  • Example 1 The difference between this embodiment and Example 1 is the ratio of the graphene-carbon nanotube composite material selected in the first step.
  • the specific preparation method is as follows:
  • Coated graphene-carbon nanoparticle prepared by example 2, example 3, example 4, and example 5 The rate performance of the material measured by charging and discharging the meter tube composite nickel-cobalt-manganese ternary material at 0.2C-2C rate is shown in Fig. 2.
  • This embodiment differs from Example 6 in the temperature of the evaporating solvent selected in the second step.
  • the specific preparation method is as follows:
  • the sample obtained in the first step that is, the coupled graphene-carbon nanotube dispersion liquid is poured into the ternary material dispersion liquid, dispersed for 10 minutes, placed in a constant temperature stirrer, and the solvent is evaporated at a low temperature of 70 ° C;
  • Example 8 This embodiment differs from Example 8 in the calcination temperature of the three materials in the step.
  • the specific preparation method is as follows:
  • 400 mesh was sieved, and then sintered in a nitrogen atmosphere, and heated to 500 ° C at 2 ° C / min, and kept for 5 hours. After natural cooling, 400 mesh was sieved after grinding to obtain a ternary material coated with a coupled carbon nanotube-graphene composite three-dimensional network structure.
  • the product obtained in the second step was ground, sieved through 400 mesh, sintered in a nitrogen atmosphere, heated to 300 ° C at 2 ° C / min, and kept for 4 hours. After natural cooling, 400 mesh was sieved after grinding to obtain a ternary material coated with a coupled carbon nanotube-graphene composite three-dimensional network structure.
  • Example 11 The other steps were the same as in Example 11 to obtain a positive electrode material in the present invention.
  • the product obtained in the second step was ground, sieved through 400 mesh, sintered in a nitrogen atmosphere, and heated to 300 ° C at 2 ° C / min, and kept for 6 hours. After natural cooling, 400 mesh was sieved after grinding to obtain a ternary material coated with a coupled carbon nanotube-graphene composite three-dimensional network structure.
  • Example 11 The other steps were the same as in Example 11 to obtain a positive electrode material in the present invention.
  • This embodiment differs from Example 1 in the amount of coating of graphene-carbon nanotubes in the first step.
  • the coating amount of graphene-carbon nanotubes in Example 1 was 0.4%.
  • 0.05 g of graphene was dispersed in an organic solvent, ultrasonically dispersed for 40 min to obtain a graphene dispersion, and then a weight ratio of 0.05 g of carbon nanotubes was added to the solution, and a small amount of a silane coupling agent was stirred for 30 minutes to obtain a coupling.
  • Graphene-carbon nanotube dispersion 1.0 g of polyvinylpyrrolidone is dissolved in 50.0 g of deionized water at normal temperature, and after physical mixing and dispersion, 50.0 g of nickel-cobalt-manganese ternary material is added and stirred for 40 minutes to obtain a ternary material.
  • the other steps were the same as in Example 1, and the positive electrode material in the present invention was obtained.
  • the coating amount of graphene-carbon nanotubes was 0.2%.
  • This embodiment differs from Example 1 in the amount of coating of graphene-carbon nanotubes in the first step.
  • the coating amount of graphene-carbon nanotubes in Example 1 was 0.4%.
  • the other steps were the same as in Example 1, and the positive electrode material in the present invention was obtained.
  • the coating amount of graphene-carbon nanotubes was 0.3%.
  • This embodiment differs from Example 1 in the amount of coating of graphene-carbon nanotubes in the first step.
  • the coating amount of graphene-carbon nanotubes in Example 1 was 0.4%.
  • the other steps were the same as in Example 1, and the positive electrode material in the present invention was obtained.
  • the coating amount of graphene-carbon nanotubes was 1.0%.
  • Example 13 The rate performance of the coupled graphene-carbon nanotube composite nickel cobalt manganese ternary material prepared in Example 1, Example 13, Example 14, and Example 15 is shown in FIG.

Abstract

The present invention relates to the technical field of battery materials, and in particular discloses a ternary material coated with a three-dimensional network structure of a coupled carbon nanotube-graphene composite and a manufacturing method thereof. The ternary material coated with the three-dimensional network structure of the coupled carbon nanotube-graphene composite is made from a nickel-cobalt-manganese ternary material, carbon nanotubes and graphene. The method comprises: using polyvinylpyrrolidone as a dispersant, and at the same time, connecting graphene and carbon nanotubes by using a silane coupling agent and via liquid-phase self-assembly to form a three-dimensional network structure thereof; and next uniformly dispersing the coupled carbon nanotube-graphene composite material and the nickel-cobalt-manganese ternary material via a physical method, then coating the surface of the nickel-cobalt-manganese ternary material, and placing in an inert atmosphere to sinter, so as to obtain a uniformly-coated product. The product of the present invention has a high specific discharge capacity, long cycle life and a simple manufacturing process facilitating mass production.

Description

偶联的碳纳米管-石墨烯复合三维网络结构包覆的三元材料及其制备方法Coupling carbon nanotube-graphene composite three-dimensional network structure coated ternary material and preparation method thereof (一)技术领域(1) Technical field
本发明涉及电池材料技术领域，特别涉及一种偶联的碳纳米管-石墨烯复合三维网络结构包覆的三元材料及其制备方法。The invention relates to the technical field of battery materials, in particular to a ternary material coated with a coupled carbon nanotube-graphene composite three-dimensional network structure and a preparation method thereof.
(二)背景技术(2) Background technology
随着科技的进步，电子产品、电动汽车、医疗设备和航天航空等领域对储能设备的要求日益提高，能量密度高、体积小、循环寿命长的锂离子电池得到了广泛应用。在满足安全、环保、成本、寿命等方面后，关键的性能指标是高能量密度和快速放电能力。例如，美、日等国对下一代锂离子动力电池的能量密度要求达到300Wh/kg，是目前正在发展的LiFePO4动力电池能量密度的2倍以上。因此提高锂离子电池能量密度的途径主要是：一、提高正极材料的比容量；二、提高正极材料的电极电势从而提高电池的工作电压。目前已经商业化的正极材料LiCoO2、LiMn2O4、LiFePO4，其实际比容量最高仅有145mAh/g，且存在成本高、安全性差、一致性差等缺点。而镍钴锰酸锂复合材料容量高，实际比容量可达200mAh/g且具有成本较低、稳定性好、安全性高等优点，近几年来，逐渐替代了部分钴酸锂。其中，Co能有效地减少阳离子混排，稳定材料的层状结构，Ni可提高材料的容量，Mn不仅可以降低材料的成本，而且可以提高材料的安全性和稳定性。因此该材料展示了优异的循环性能，获得了市场的认可。With the advancement of technology, the requirements for energy storage equipment in the fields of electronic products, electric vehicles, medical equipment and aerospace are increasing. Lithium-ion batteries with high energy density, small volume and long cycle life have been widely used. After meeting safety, environmental protection, cost, and life, key performance indicators are high energy density and fast discharge capability. For example, countries such as the United States and Japan have an energy density requirement of 300 Wh/kg for the next-generation lithium-ion power battery, which is more than twice the energy density of the LiFePO 4 power battery currently under development. Therefore, the ways to improve the energy density of the lithium ion battery are mainly: first, to increase the specific capacity of the positive electrode material; second, to increase the electrode potential of the positive electrode material to improve the operating voltage of the battery. The cathode materials LiCoO 2 , LiMn 2 O 4 and LiFePO 4 which have been commercialized at present have the actual specific capacity of only 145 mAh/g, and have the disadvantages of high cost, poor safety and poor consistency. The nickel-cobalt-manganese composite material has a high capacity, the actual specific capacity can reach 200 mAh/g and has the advantages of low cost, good stability and high safety. In recent years, some lithium cobalt oxide has been gradually replaced. Among them, Co can effectively reduce the cation mixing, stabilize the layered structure of the material, Ni can increase the capacity of the material, Mn can not only reduce the cost of the material, but also improve the safety and stability of the material. As a result, the material demonstrates excellent cycle performance and is recognized by the market.
镍钴锰酸锂三元材料自2001年开始研究以来，以其稳定的比容量、较好的安全性和结构稳定性以及适中的成本，迅速被产业化，特别是当钴价格较高时，其成本优势更为明显。目前三元材料主要应用于钢壳或者铝壳的圆柱形与方形锂离子电池中。就应用来说，镍钴锰酸锂三元材料大多应用于移动电源、功能型手机及电动自行车等对能量密度要求不高的领域。在智能手机和平板电脑等领域，目前主要是钴酸锂，主要是因为三元材料存在压实密度低、易于气胀等缺点，其在动力型锂离子电池、高电压体系锂电池中的应用目前还处于研发阶段。而未来五年镍钴锰酸锂材料是研发和产业化的主流，也是最具有潜力成为下一代动力型锂离子电池和电子产品用高能量密度小型锂离子电池正极材料。而高密度化和高电压化的镍钴锰酸锂三元材料对环境及设备要求较低，制备加工难度较小，一致性和可靠性高，并且能达到高能量密度的目标。Since its research in 2001, lithium nickel cobalt manganese ternary materials have been rapidly industrialized due to their stable specific capacity, good safety and structural stability, and moderate cost, especially when the price of cobalt is high. Its cost advantage is more obvious. At present, ternary materials are mainly used in cylindrical and square lithium ion batteries of steel or aluminum. For applications, lithium nickel cobalt manganese ternary materials are mostly used in mobile power, functional mobile phones and electric bicycles where energy density is not critical. In the fields of smart phones and tablets, Lithium Cobaltate is mainly used, mainly because of the shortcomings of low density, easy to expand, etc. in ternary materials, and its application in power lithium-ion batteries and high-voltage system lithium batteries. It is still in the research and development stage. In the next five years, lithium nickel cobalt manganese oxide material is the mainstream of R&D and industrialization, and it is also the cathode material with high potential and high energy density small lithium ion battery for the next generation of power lithium-ion batteries and electronic products. The high-density and high-voltage nickel-cobalt-manganese ternary materials have lower requirements on environment and equipment, are less difficult to prepare and process, have high consistency and reliability, and can achieve high energy density targets.
经长期研究，该材料虽具有良好的电化学性能，但就实用性而言，仍有问题亟需解决。三元材料在首周脱锂后，易引起失氧和相变，导致较大的首周不可逆损失。此外，该材料导电率低，大倍率性能不佳。且三元材料容易在锂层中发生阳离子混排，在宽的放电电压范围内容易使有机电解液与电极材料发生强烈的副反应，增加电池在充放电过程中的阻抗，降低材料的电化学性能。 After long-term research, although the material has good electrochemical performance, in terms of practicality, there are still problems to be solved. After the ternary material is delithized in the first week, it is easy to cause oxygen loss and phase change, resulting in a large first week irreversible loss. In addition, the material has low electrical conductivity and poor macro-rate performance. Moreover, the ternary material is easily cation-discharged in the lithium layer, and the organic electrolyte and the electrode material are easily reacted strongly in a wide discharge voltage range, thereby increasing the impedance of the battery during charging and discharging, and reducing the electrochemical of the material. performance.
为了改进三元材料的性能，科研人员不论从材料的制备方法上，还是材料的掺杂改性或者包覆改性上都做了大量扎实的研究工作。材料的制备方法包括高温固相法、共沉淀法、溶胶凝胶法、水热法、喷雾干燥法、控制结晶沉淀法等，此外，通过适当的掺杂可以使三元材料的结构更稳定，减小离子混排效应，并且能有效的改善材料的循环性能。掺杂的元素要可以进入要取代离子的位置，掺杂离子的半径和要取代的离子要有相近的半径以保证材料结构的稳定，掺杂的离子本身要具有很好的稳定性，不和电解液发生反应，不会发生氧化还原反应。掺杂分为阴离子掺杂和阳离子掺杂。阳离子的掺杂元素有Ti、Mg、Al、Cr、Zr和稀土元素等，阴离子掺杂多为卤族元素，掺杂较多的是F-离子。其次，对三元材料进行表面包覆也是目前研究的一大热点，它是指在材料的表面包覆一层薄膜物质，薄膜物质一般不改变材料本身的结构，通过包覆可以提高材料的导电率，减少电解液对材料的侵蚀，从而改善材料的循环性能和倍率性能。表面包覆的手段包括氧化物包覆、磷酸盐包覆、氟化物包覆、锂离子电池正极材料包覆以及碳包覆。这里重点碳包覆，Guo R等人采用具有低裂解温度的PVA成功合成了碳包覆的镍钴锰三元材料，并对其碳含量进行了优化，当碳含量为1.0wt％时，材料的循环性能和倍率性能比未包覆的材料有很大的提高。Sinha N.N等采用一步法并以葡萄糖为碳源合成了碳包覆的亚微米级镍钴锰三元材料前驱体，并于900℃合成6h得到了镍钴锰酸锂晶体。研究表面其碳包覆层具有优异的循环性能，并且大大抑制了高倍率放电时的容量衰减。Rao等通过微乳液法制备LiCo1/3Ni1/3Mn1/3O2，再通过球磨制备了LiCo1/3Ni1/3Mn1/3O2石墨烯复合物。以1C、5C充放电首周放电比容量分别为172mAh/g和153mAh/g，材料的性能得到提高。中科院过程所通过球磨的方法将石墨烯和三元材料进行复合，3C充放电时，循环20周之后容量保持率为82％。In order to improve the performance of ternary materials, researchers have done a lot of solid research work on the preparation methods of materials, doping modification or coating modification of materials. The preparation method of the material includes a high temperature solid phase method, a coprecipitation method, a sol gel method, a hydrothermal method, a spray drying method, a controlled crystal precipitation method, and the like, and further, the structure of the ternary material can be made more stable by appropriate doping. The ion mixing effect is reduced, and the cycle performance of the material can be effectively improved. The doped element should enter the position where the ion is to be replaced. The radius of the doping ion and the ion to be replaced should have similar radii to ensure the stability of the material structure. The doped ions themselves must have good stability. The electrolyte reacts and no redox reaction occurs. Doping is divided into anion doping and cation doping. The doping elements of the cation are Ti, Mg, Al, Cr, Zr and rare earth elements, etc., the anion doping is mostly a halogen element, and the doping is more F - ion. Secondly, surface coating of ternary materials is also a hot topic in current research. It refers to coating a film material on the surface of the material. The film material generally does not change the structure of the material itself, and the coating can improve the conductivity of the material. Rate, reduce the erosion of the material by the electrolyte, thereby improving the cycle performance and rate performance of the material. The means for surface coating include oxide coating, phosphate coating, fluoride coating, lithium ion battery cathode material coating, and carbon coating. Here, the key carbon coating, Guo R et al. successfully synthesized carbon-coated nickel-cobalt-manganese ternary materials using PVA with low cracking temperature, and optimized its carbon content. When the carbon content is 1.0wt%, the material The cycle performance and rate performance are greatly improved compared to uncoated materials. Sinha NN et al. synthesized a carbon-coated submicron-sized nickel-cobalt-manganese ternary material precursor using a one-step method and using glucose as a carbon source. The nickel-cobalt-manganese hydride crystal was obtained by synthesizing at 900 ° C for 6 h. The carbon coating on the surface of the study has excellent cycle performance and greatly suppresses the capacity decay at high rate discharge. Rao et al. prepared LiCo 1/3 Ni 1/3 Mn 1/3 O 2 by microemulsion method, and then prepared LiCo 1/3 Ni 1/3 Mn 1/3 O 2 graphene composite by ball milling. The specific discharge capacity at the first week of 1C and 5C charge and discharge was 172 mAh/g and 153 mAh/g, respectively, and the performance of the material was improved. In the process of the Chinese Academy of Sciences, the graphene and the ternary materials were combined by ball milling. When the 3C was charged and discharged, the capacity retention rate was 82% after 20 weeks of circulation.
以上的碳包覆效果不是很明显，石墨烯包覆比传统的碳包覆更好地提高了材料的电化学性能。且石墨烯/碳纳米管包覆的三元材料的开发有助于在电池储能及动力电车领域取得重大突破。The above carbon coating effect is not very obvious, and the graphene coating improves the electrochemical performance of the material better than the conventional carbon coating. The development of graphene/carbon nanotube coated ternary materials has contributed to major breakthroughs in battery energy storage and power trams.
(三)发明内容(3) Invention content
本发明为了弥补现有技术的不足，提供了一种提高材料的锂离子扩散系数和电子电导率、抑制材料在高倍率放电的容量衰减的偶联的碳纳米管-石墨烯复合三维网络结构包覆的三元材料及其制备方法。In order to make up for the deficiencies of the prior art, the present invention provides a coupled carbon nanotube-graphene composite three-dimensional network structure package for improving the lithium ion diffusion coefficient and electronic conductivity of a material and suppressing the capacity attenuation of a material at a high rate discharge. Covered ternary materials and preparation methods thereof.
本发明是通过如下技术方案实现的：The invention is achieved by the following technical solutions:
一种偶联的碳纳米管-石墨烯复合三维网络结构包覆的三元材料，以镍钴锰三元材料、碳纳米管和石墨烯为原料，其特征在于：以聚乙烯吡咯烷酮为分散剂，同时通过液相自组合的方式采用硅烷偶联剂来连接石墨烯和碳纳米管，使其形成三维网络结构，然后将偶联的碳纳米管-石墨烯复合材料和镍钴锰三元材料通过物理方法分散均匀后，包覆在镍钴锰三元材料的表面，置于惰性气氛中烧结得到均匀包覆的产品。A coupled carbon nanotube-graphene composite three-dimensional network structure coated ternary material, using nickel-cobalt-manganese ternary material, carbon nanotubes and graphene as raw materials, characterized in that polyvinylpyrrolidone is used as a dispersing agent At the same time, the silane coupling agent is used to connect the graphene and the carbon nanotubes by a liquid phase self-combination method to form a three-dimensional network structure, and then the coupled carbon nanotube-graphene composite material and the nickel cobalt manganese ternary material are formed. After being uniformly dispersed by a physical method, it is coated on the surface of the nickel-cobalt-manganese ternary material, and is sintered in an inert atmosphere to obtain a uniformly coated product.
本发明为了克服现有的镍钴锰三元材料中电导率低和锂离子扩散系数小， 电池倍率充放电性能差的问题，采用的技术方案为，石墨烯强的电子导电性，减少了电极活性材料与电解液之间的界面电阻，有利于Li+的传导；二维结构的石墨烯片层包覆在电极材料表面，抑制了金属氧化物的溶解和相变，保持了充放电过程中电极材料的结构稳定。一维结构的碳纳米管为锂离子和电子的传导提供了优异的传输通道，且电导率较高。为了充分利用石墨烯和碳纳米管独特的性能，本项目利用硅烷偶联剂将这两种碳组合成的三维网状结构来包覆三元材料，利用该复合碳特有的小尺寸效应和表面效应，以及自身的范德华作用力来控制三元材料颗粒在纳米尺度内，并能增加活性物质之间的接触，提高整体电极的电导，有利于锂离子和电子在材料中的快速储存和传输，降低了极化过程，提高循环性能。The invention overcomes the problems of low conductivity and small lithium ion diffusion coefficient and poor battery charge and discharge performance in the existing nickel-cobalt-manganese ternary material, and adopts the technical scheme that the graphene has strong electronic conductivity and reduces the electrode. The interface resistance between the active material and the electrolyte is favorable for the conduction of Li + ; the two-dimensional structure of the graphene sheet is coated on the surface of the electrode material, inhibiting the dissolution and phase transformation of the metal oxide, and maintaining the charge and discharge process. The structure of the electrode material is stable. One-dimensional carbon nanotubes provide excellent transport channels for lithium ion and electron conduction, and have high electrical conductivity. In order to make full use of the unique properties of graphene and carbon nanotubes, this project uses a silane coupling agent to combine the two carbons into a three-dimensional network structure to coat the ternary material, utilizing the small size effect and surface unique to the composite carbon. The effect, as well as its own van der Waals force, controls the ternary material particles at the nanometer scale, and can increase the contact between the active materials, improve the conductance of the overall electrode, and facilitate the rapid storage and transport of lithium ions and electrons in the material. Reduce the polarization process and improve cycle performance.
本发明所述的三元材料的制备方法，包括如下步骤：The preparation method of the ternary material according to the present invention comprises the following steps:
(1)常温下，将重量比为0.1-1％的石墨烯分散在有机溶剂中，超声分散40min得到石墨烯分散液，然后想溶液中加入重量比为0.2-0.8％的碳纳米管以及少量的硅烷偶联剂，搅拌30min得到偶联的石墨烯-碳纳米管分散液；(1) At room temperature, graphene with a weight ratio of 0.1-1% is dispersed in an organic solvent, ultrasonically dispersed for 40 minutes to obtain a graphene dispersion, and then a weight ratio of 0.2-0.8% of carbon nanotubes and a small amount are added to the solution. a silane coupling agent, stirred for 30 min to obtain a coupled graphene-carbon nanotube dispersion;
(2)常温下，将重量比为2％的聚乙烯吡咯烷酮溶于去离子水中，物理混合分散均匀后，加入镍钴锰三元材料，搅拌40min得到三元材料分散液；(2) Dissolving polyvinylpyrrolidone with a weight ratio of 2% at room temperature in deionized water, physically mixing and dispersing uniformly, adding nickel-cobalt-manganese ternary material, stirring for 40 minutes to obtain a ternary material dispersion;
(3)将上述偶联的石墨烯-碳纳米管分散液导入三元材料分散液中，分散10min后，置于恒温搅拌器中，60-80℃下搅拌蒸发掉溶剂；(3) introducing the above-mentioned coupled graphene-carbon nanotube dispersion into a ternary material dispersion, dispersing for 10 minutes, placing it in a thermostat stirrer, and evaporating the solvent under stirring at 60-80 ° C;
(4)将蒸发溶剂后的产物研磨后，400目过筛，然后置于保护气氛中于250-500℃下烧结3-6h，研磨过筛后得到产品。(4) After the product obtained by evaporating the solvent is ground, sieved through 400 mesh, and then sintered in a protective atmosphere at 250-500 ° C for 3-6 h, and sieved to obtain a product.
其优选的技术方案为：Its preferred technical solution is:
所述石墨烯的比表面积为500-1000m2/g，其纳米片层数为2-6层，其导电性较好；碳纳米管的比表面积为40-70m2/g，其粒径为60-100nm，其导电率较高；石墨烯与碳纳米管的质量比为1:1-5。The graphene has a specific surface area of 500-1000 m 2 /g, and the number of nanosheet layers is 2-6 layers, and the conductivity thereof is good; the specific surface area of the carbon nanotubes is 40-70 m 2 /g, and the particle diameter thereof is 60-100nm, its conductivity is higher; the mass ratio of graphene to carbon nanotubes is 1:1-5.
所述步骤(1)中，石墨烯的重量比为0.1-0.5％，碳纳米管的重量比为0.2-0.5％。In the step (1), the weight ratio of graphene is 0.1-0.5%, and the weight ratio of carbon nanotubes is 0.2-0.5%.
步骤(1)中，有机溶剂为乙醇、异丙醇、正丁醇、丙三醇、甲醇、N-甲基吡咯烷酮和丙酮中的一种或两种。In the step (1), the organic solvent is one or both of ethanol, isopropanol, n-butanol, glycerin, methanol, N-methylpyrrolidone and acetone.
步骤(2)中，物理混合方式为搅拌、超声和高速剪切乳化中的一种或多种。In the step (2), the physical mixing mode is one or more of stirring, ultrasonication, and high-speed shear emulsification.
步骤(4)中，保护气氛为氮气气氛或氩气气氛。In the step (4), the protective atmosphere is a nitrogen atmosphere or an argon atmosphere.
与现有技术相比，本发明采用液相自组装的方法获得了具有三维网状结构的石墨烯-碳纳米管复合碳材料，并将其包覆在镍钴锰三元材料的表面。一方面，导电剂石墨烯-碳纳米管复合材料的添加，降低了电极活性材料与电解液之间的界面电阻，有利于Li+的传导，提高了材料的导电性和锂离子扩散系数；另一方面，三维网状结构的石墨烯-碳纳米管均匀地包覆三元材料的表面，可以抑制材料的自团聚，并能增加活性物质之间的接触，保证循环过程中电子离子双通道畅通，提高整体电极的电导，降低电池充放电过程中的极化过程，提高电池的循环性能。 Compared with the prior art, the present invention obtains a graphene-carbon nanotube composite carbon material having a three-dimensional network structure by a liquid phase self-assembly method, and coats the surface of the nickel-cobalt-manganese ternary material. On the one hand, the addition of the conductive agent graphene-carbon nanotube composite material reduces the interface resistance between the electrode active material and the electrolyte, facilitates the conduction of Li + , improves the conductivity of the material and the lithium ion diffusion coefficient; On the one hand, the three-dimensional network structure of graphene-carbon nanotubes uniformly coats the surface of the ternary material, can inhibit the self-agglomeration of the material, and can increase the contact between the active materials, thereby ensuring the smooth passage of the electron ions in the circulation process. Improve the conductance of the whole electrode, reduce the polarization process during battery charging and discharging, and improve the cycle performance of the battery.
复合0.4％的石墨烯-碳纳米管复合碳材料，0.2C倍率下首周放电容量达172.5mAh/g，1C倍率下首周放电容量为158.2mAh/g，比原材料高15mAh/g左右，循环110周后，容量保持率达87.2％，且8C倍率循环下，容量仍高达129.5mAh/g，提高了材料的循环稳定性和倍率性能。The composite of 0.4% graphene-carbon nanotube composite carbon material has a discharge capacity of 172.5 mAh/g in the first week at a rate of 0.2 C, and a discharge capacity of 158.2 mAh/g in the first week at a rate of 15 C, which is about 15 mAh/g higher than the raw material. After 110 weeks, the capacity retention rate reached 87.2%, and the capacity was still as high as 129.5 mAh/g under the 8C rate cycle, which improved the cycle stability and rate performance of the material.
此外，碳纳米管的添加，降低了生产成本，使该新材料在电池储能及动力电车领域的拓展应用具有重大的理论指导意义和工程应用价值。该方法工艺简单、操作方便，易于规模化生产。In addition, the addition of carbon nanotubes reduces the production cost, and the new material has great theoretical guiding significance and engineering application value in the field of battery energy storage and power tram. The method is simple in process, convenient in operation and easy to scale production.
本发明属于电化学电池领域，所述的产品具有高的放电比容量机长循环寿命，其制备过程简单，易于规模化生产。The invention belongs to the field of electrochemical cells, and the product has a high discharge specific capacity and a long cycle life, and the preparation process is simple and easy to scale production.
(四)附图说明(4) Description of the drawings
下面结合附图对本发明作进一步的说明。The invention will now be further described with reference to the accompanying drawings.
图1为复合不同包覆量的石墨烯-碳纳米管后所制备的复合三元材料的倍率性能图；1 is a graph showing the rate performance of a composite ternary material prepared by combining different coating amounts of graphene-carbon nanotubes;
图2为复合不同比例的石墨烯-碳纳米管后所制备的复合三元材料的倍率性能图；2 is a graph showing the rate performance of a composite ternary material prepared by combining graphene-carbon nanotubes in different proportions;
图3为复合不同比例石墨烯-碳纳米管以及纯石墨烯的材料和原材料的倍率放电对比图；3 is a comparison diagram of rate discharge of materials and raw materials of composite graphene-carbon nanotubes and pure graphene;
图4为复合不同比例石墨烯-碳纳米管以及纯石墨烯的材料和原材料在1C倍率下的循环寿命图；4 is a cycle life diagram of materials and raw materials of composite graphene-carbon nanotubes and pure graphene at a ratio of 1 C;
图5为复合石墨烯-碳纳米管后，材料的扫描电镜图；Figure 5 is a scanning electron micrograph of the material after composite graphene-carbon nanotubes;
图6为石墨烯-碳纳米管复合三元材料及原材料的XRD图。Fig. 6 is an XRD chart of a graphene-carbon nanotube composite ternary material and a raw material.
(五)具体实施方式(5) Specific implementation methods
下面结合实施例对本发明作进一步说明。以下实施例用于说明本发明，但不用来限制本发明的范围。The invention is further illustrated by the following examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
实施例1：Example 1:
(1)将0.1g的石墨烯分散在有机溶剂中，超声分散40min得到石墨烯分散液，然后向溶液中加入重量比为0.1g的碳纳米管，以及少量的硅烷偶联剂，搅拌30min，得到偶联的石墨烯-碳纳米管分散液；常温下，将1.0g聚乙烯吡咯烷酮溶于50.0g去离子水中，物理混合分散均匀后，加入50.0g镍钴锰三元材料，搅拌40min，得到三元材料分散液；(1) 0.1 g of graphene is dispersed in an organic solvent, ultrasonically dispersed for 40 min to obtain a graphene dispersion, and then a weight ratio of 0.1 g of carbon nanotubes, and a small amount of a silane coupling agent are added to the solution, and stirred for 30 minutes. The coupled graphene-carbon nanotube dispersion liquid is obtained; 1.0 g of polyvinylpyrrolidone is dissolved in 50.0 g of deionized water at normal temperature, and after physical mixing and dispersion, 50.0 g of nickel-cobalt-manganese ternary material is added and stirred for 40 minutes. Ternary material dispersion;
(2)将偶联的石墨烯-碳纳米管分散液倒入三元材料分散液中，分散10min后，置于恒温搅拌器中，80℃搅拌蒸发掉溶剂；(2) Pour the coupled graphene-carbon nanotube dispersion into the ternary material dispersion, disperse for 10 min, place in a constant temperature stirrer, and evaporate the solvent at 80 ° C with stirring;
(3)将上述产物研磨后，400目过筛，后置于氮气气氛中烧结，以2℃/min升温至300℃，并保温5小时。自然冷却后，研磨后400目过筛得到偶联的碳纳米管-石墨烯复合三维网络结构包覆的三元材料。(3) After grinding the above product, 400 mesh was sieved, and then sintered in a nitrogen atmosphere, and heated to 300 ° C at 2 ° C / min, and kept for 5 hours. After natural cooling, 400 mesh was sieved after grinding to obtain a ternary material coated with a coupled carbon nanotube-graphene composite three-dimensional network structure.
采用武汉蓝电CT2001A充放电仪进行恒流充放电测试锂电池正极材料的电化学性能。实验电池是在充满氩气的手套箱中进行，使用的电解液为LiPF6/EC+DMC+EMC(体积比1：1：1)，隔膜为Celgard 2400型隔膜；对电极为金属锂片。材料的电化学性能采用CR2032型纽扣电池进行考察。 The electrochemical performance of the cathode material of lithium battery was tested by constant current charge and discharge using Wuhan Landian CT2001A charge and discharge instrument. The test cell was carried out in an argon-filled glove box using an electrolyte of LiPF 6 /EC+DMC+EMC (volume ratio 1:1:1), a separator of Celgard 2400 type diaphragm, and a counter electrode of metallic lithium sheet. The electrochemical performance of the material was investigated using a CR2032 coin cell battery.
将PVDF溶于NMP中，制备质量分数为4％的PVDF溶液，搅拌均匀并置于烘箱中80℃干燥12h后备用。分别将实施例1中包覆后所得的产物和所用的镍钴锰原材料、导电碳黑Super P、导电碳黑KS和上述PVDF溶液按照质量比88:3:3:6混合，充分搅拌后，将浆液均匀涂布在铝箔上，120℃真空干燥12h后用双辊压片机碾压。用冲片机制成直径为10mm的电极片，然后将电极片称重，120℃真空干燥5h，放置于手套箱中，组装成CR2032型纽扣电池，将扣式电池放置8h后进行充放电测试。PVDF was dissolved in NMP to prepare a PVDF solution with a mass fraction of 4%, stirred well and placed in an oven at 80 ° C for 12 h for use. The product obtained by coating in Example 1 and the nickel-cobalt-manganese raw material used, the conductive carbon black Super P, the conductive carbon black KS and the above PVDF solution were respectively mixed at a mass ratio of 88:3:3:6, and after sufficiently stirring, The slurry was uniformly coated on an aluminum foil, vacuum dried at 120 ° C for 12 hours, and then compacted by a two-roll tablet press. The electrode piece with a diameter of 10 mm was made by a punching machine, and then the electrode piece was weighed, vacuum dried at 120 ° C for 5 hours, placed in a glove box, assembled into a CR2032 type button battery, and the button type battery was placed for 8 hours, and then subjected to a charge and discharge test.
循环性能曲线：在25±1℃下，电压范围为3.0-4.3V(Vs Li+/Li)下对电池进行恒流充放电测试。图4中的Gs-CNTs(11)@LNCM曲线为实施例1复合石墨烯-碳纳米管材料后在1C倍率下的循环寿命图，前两周是在0.2C恒流充放电下对材料进行活化处理。在0.2C倍率充放电时，实施例1产物的首次放电比容量为172.5mAh/g，而原材料的首次放电比容量为168.5mAh/g。故在0.2C充放电下，首次放电比容量仅相差4mAh/g，效果不明显。但在1C倍率充放电下，实施例1产物得首次放电比容量为158.2mAh/g，且循环100周后，容量保持率为87.2％。而原材料的首次放电比容量为142mAh/g,循环100周后，容量保持率为81.5％。即在1C充放电时，循环100周之后，实施例1所制备的材料的放电比容量比原材料的放电比容量高22mAh/g。说明包覆后，实施例1产物得正极部分的锂离子活动性更高，相对于原材料而言，锂离子的嵌入脱出更容易。由此可见，使用石墨烯-碳纳米管对镍钴锰正极材料进行修饰后，降低了电池内部的极化过程，提高了材料的循环稳定性。Cyclic performance curve: The battery was subjected to constant current charge and discharge test at a voltage range of 3.0-4.3 V (Vs Li + /Li) at 25 ± 1 °C. The Gs-CNTs(11)@LNCM curve in Fig. 4 is the cycle life diagram of the composite graphene-carbon nanotube material of Example 1 at 1C rate, and the material is subjected to the constant current charge and discharge at 0.2C for the first two weeks. Activation treatment. The first discharge specific capacity of the product of Example 1 was 172.5 mAh/g at a charge and discharge rate of 0.2 C, and the first discharge specific capacity of the raw material was 168.5 mAh/g. Therefore, under the charge and discharge of 0.2C, the first discharge specific difference is only 4mAh/g, and the effect is not obvious. However, the product of Example 1 had a first discharge specific capacity of 158.2 mAh/g at 1 C rate charge and discharge, and the capacity retention rate was 87.2% after 100 cycles. The first discharge specific capacity of the raw material was 142 mAh/g, and after 100 cycles, the capacity retention rate was 81.5%. That is, at the time of 1 C charge and discharge, the discharge specific capacity of the material prepared in Example 1 was higher than the discharge specific capacity of the raw material by 22 mAh/g after 100 cycles. It is shown that the lithium ion activity of the positive electrode portion of the product of Example 1 is higher after coating, and the insertion and extraction of lithium ions is easier with respect to the raw material. It can be seen that the modification of the nickel-cobalt-manganese cathode material by using graphene-carbon nanotubes reduces the polarization process inside the battery and improves the cycle stability of the material.
倍率性能曲线：在3.0-4.3V(Vs Li+/Li)电压范围内，对电池进行恒流充放电测试。图3中Gs-CNTs(11)@LNCM曲线为实施例1复合石墨烯-碳纳米管后，材料的倍率性能图。在0.5C和1C倍率放电电流下，两组电池放电比容量都比较接近，分别为165.5和161.2mAh/g，当以2C和5C电流放电时两组的差距比较明显，复合之后的材料的放电比容量分别为149.9和129.5mAh/g，且8C电流放电时，材料的放电比容量仍能达到99.4mAh/g。而没有复合石墨烯-碳纳米管的材料，以5C和8C电流放电时，材料的放电比容量分别仅有96.3mAh/g和52.1mAh/g，表明复合石墨烯后材料的高倍率放电性能明显提高，增强了镍钴锰三元材料的抗衰减能力。Rate performance curve: The battery is subjected to constant current charge and discharge test in the range of 3.0-4.3V (Vs Li+/Li). The Gs-CNTs(11)@LNCM curve in Fig. 3 is a graph showing the rate performance of the material after the composite graphene-carbon nanotube of Example 1. At 0.5C and 1C rate discharge current, the discharge specific capacities of the two groups are relatively close, which are 165.5 and 161.2 mAh/g, respectively. When the current is discharged at 2C and 5C, the difference between the two groups is obvious, and the discharge of the material after the composite is obvious. The specific capacity is 149.9 and 129.5 mAh/g, and the discharge specific capacity of the material can still reach 99.4 mAh/g when the current is discharged at 8C. When there is no composite graphene-carbon nanotube material, the discharge specific capacity of the material is only 96.3 mAh/g and 52.1 mAh/g when discharged at 5C and 8C, respectively, indicating that the high rate discharge performance of the composite graphene material is obvious. Improve and enhance the anti-attenuation ability of nickel-cobalt-manganese ternary materials.
复合石墨烯-碳纳米管后，材料的扫描电镜图如图5所示，复合之后，可清晰的看出，石墨烯和碳纳米管形成了一个三维网状结构，包裹在镍钴锰三元材料颗粒的中间，抑制了材料的自团聚，并增加了活性物质之间的接触。After composite graphene-carbon nanotubes, the scanning electron micrograph of the material is shown in Fig. 5. After compounding, it can be clearly seen that graphene and carbon nanotubes form a three-dimensional network structure wrapped in nickel-cobalt-manganese ternary The middle of the material particles inhibits the self-agglomeration of the material and increases the contact between the active materials.
复合石墨烯-碳纳米管后，材料的XRD图如图6所示。包覆之后，对材料的结构没有太大影响，(003)峰和(104)峰的强度之比I(003)/I(104)分别为1.199，1.241，这一比值经常被用来衡量镍钴锰三元材料的锂镍混排程度，当I(003)/I(104)大于1.2时，材料具有较低的锂镍混排程度，可看出，包覆后，更有利于锂离子的可逆脱嵌。After composite graphene-carbon nanotubes, the XRD pattern of the material is shown in Fig. 6. After coating, the structure of the material is not greatly affected. The ratio of the intensity of the (003) peak to the (104) peak I (003) / I (104) is 1.199, 1.241, respectively. This ratio is often used to measure nickel. The degree of lithium-nickel mixing of cobalt-manganese ternary materials, when I (003) /I (104) is greater than 1.2, the material has a lower degree of lithium nickel mixed discharge, it can be seen that after coating, it is more favorable for lithium ion Reversible deintercalation.
实施例2：Example 2:
本实施方式与实施例1不同的是步骤一中所选用的石墨烯-碳纳米管复合 材料的比例。具体制备方法如下：The difference between this embodiment and the first embodiment is the graphene-carbon nanotube composite selected in the first step. The ratio of materials. The specific preparation method is as follows:
将0.067g的石墨烯分散在有机溶剂中，超声分散40min得到石墨烯分散液然后向溶液中加入重量比为0.133g的碳纳米管，以及少量的硅烷偶联剂，搅拌30min，得到偶联的石墨烯-碳纳米管分散液；常温下，将1.0g聚乙烯吡咯烷酮溶于50.0g去离子水中，物理混合分散均匀后，加入50.0g镍钴锰三元材料，搅拌40min，得到三元材料分散液；0.067 g of graphene was dispersed in an organic solvent, ultrasonically dispersed for 40 min to obtain a graphene dispersion, and then a weight ratio of 0.133 g of carbon nanotubes was added to the solution, and a small amount of a silane coupling agent was stirred for 30 minutes to obtain a coupled. Graphene-carbon nanotube dispersion; 1.0g of polyvinylpyrrolidone is dissolved in 50.0g of deionized water at normal temperature, and after physical mixing and dispersion, 50.0g of nickel-cobalt-manganese ternary material is added and stirred for 40 minutes to obtain ternary material dispersion. liquid;
其他步骤与实施例1相同，得到本发明中的正极材料，即Gs-CNTs(12)@LNCM。The other steps were the same as in Example 1, and the positive electrode material of the present invention, that is, Gs-CNTs (12) @ LNCM was obtained.
实施例3：Example 3:
本实施方式与实施例1不同的是步骤一中所选用的石墨烯-碳纳米管复合材料的比例。具体制备方法如下：The difference between this embodiment and Example 1 is the ratio of the graphene-carbon nanotube composite material selected in the first step. The specific preparation method is as follows:
将0.05g的石墨烯分散在有机溶剂中，声分散40min得到石墨烯分散液然后向溶液中加入重量比为0.15g的碳纳米管，以及少量的硅烷偶联剂，搅拌30min，得到偶联的石墨烯-碳纳米管分散液；常温下，将1.0g聚乙烯吡咯烷酮溶于50.0g去离子水中，物理混合分散均匀后，加入50.0g镍钴锰三元材料，搅拌40min，得到三元材料分散液；0.05 g of graphene was dispersed in an organic solvent, acoustically dispersed for 40 min to obtain a graphene dispersion, and then a weight ratio of 0.15 g of carbon nanotubes was added to the solution, and a small amount of a silane coupling agent was stirred for 30 minutes to obtain a coupled Graphene-carbon nanotube dispersion; 1.0g of polyvinylpyrrolidone is dissolved in 50.0g of deionized water at normal temperature, and after physical mixing and dispersion, 50.0g of nickel-cobalt-manganese ternary material is added and stirred for 40 minutes to obtain ternary material dispersion. liquid;
其他步骤与实施例1相同，得到本发明中的正极材料，即Gs-CNTs(13)@LNCM。The other steps were the same as in Example 1, and the positive electrode material of the present invention, that is, Gs-CNTs (13) @ LNCM was obtained.
实施例4：Example 4:
本实施方式与实施例1不同的是步骤一中所选用的石墨烯-碳纳米管复合材料的比例。具体制备方法如下：The difference between this embodiment and Example 1 is the ratio of the graphene-carbon nanotube composite material selected in the first step. The specific preparation method is as follows:
将0.04g的石墨烯分散在有机溶剂中，声分散40min得到石墨烯分散液然后向溶液中加入重量比为0.16g的碳纳米管，以及少量的硅烷偶联剂，搅拌30min，得到偶联的石墨烯-碳纳米管分散液；常温下，将1.0g聚乙烯吡咯烷酮溶于50.0g去离子水中，物理混合分散均匀后，加入50.0g镍钴锰三元材料，搅拌40min，得到三元材料分散液；0.04 g of graphene was dispersed in an organic solvent, acoustically dispersed for 40 min to obtain a graphene dispersion, and then a weight ratio of 0.16 g of carbon nanotubes was added to the solution, and a small amount of a silane coupling agent was stirred for 30 minutes to obtain a coupled Graphene-carbon nanotube dispersion; 1.0g of polyvinylpyrrolidone is dissolved in 50.0g of deionized water at normal temperature, and after physical mixing and dispersion, 50.0g of nickel-cobalt-manganese ternary material is added and stirred for 40 minutes to obtain ternary material dispersion. liquid;
其他步骤与实施例1相同，得到本发明中的正极材料，即Gs-CNTs(14)@LNCM。The other steps were the same as in Example 1, and the positive electrode material of the present invention, that is, Gs-CNTs (14) @ LNCM was obtained.
实施例5：Example 5:
本实施方式与实施例1不同的是步骤一中所选用的石墨烯-碳纳米管复合材料的比例。具体制备方法如下：The difference between this embodiment and Example 1 is the ratio of the graphene-carbon nanotube composite material selected in the first step. The specific preparation method is as follows:
将0.033g的石墨烯分散在有机溶剂中，声分散40min得到石墨烯分散液然后向溶液中加入重量比为0.166g的碳纳米管，以及少量的硅烷偶联剂，搅拌30min，得到偶联的石墨烯-碳纳米管分散液；常温下，将1.0g聚乙烯吡咯烷酮溶于50.0g去离子水中，物理混合分散均匀后，加入50.0g镍钴锰三元材料，搅拌40min，得到三元材料分散液；0.033 g of graphene was dispersed in an organic solvent, acoustically dispersed for 40 min to obtain a graphene dispersion, and then a weight ratio of 0.166 g of carbon nanotubes was added to the solution, and a small amount of a silane coupling agent was stirred for 30 minutes to obtain a coupled Graphene-carbon nanotube dispersion; 1.0g of polyvinylpyrrolidone is dissolved in 50.0g of deionized water at normal temperature, and after physical mixing and dispersion, 50.0g of nickel-cobalt-manganese ternary material is added and stirred for 40 minutes to obtain ternary material dispersion. liquid;
其他步骤与实施例1相同，得到本发明中的正极材料，即Gs-CNTs(15)@LNCM。The other steps were the same as in Example 1, and the positive electrode material of the present invention, that is, Gs-CNTs (15) @ LNCM was obtained.
由实施例2、实施例3、实施例4、实施例5所制备的偶联的石墨烯-碳纳 米管复合镍钴锰三元材料在0.2C-2C倍率下充放电时所测得的材料的倍率性能图如图2所示。Coated graphene-carbon nanoparticle prepared by example 2, example 3, example 4, and example 5 The rate performance of the material measured by charging and discharging the meter tube composite nickel-cobalt-manganese ternary material at 0.2C-2C rate is shown in Fig. 2.
实施例6：Example 6
(1)将0.067g的石墨烯分散在有机溶剂中，超声分散40min得到石墨烯分散液，然后向溶液中加入重量比为0.133g的碳纳米管，以及少量的硅烷偶联剂，搅拌30min，得到偶联的石墨烯-碳纳米管分散液；常温下，将1.0g聚乙烯吡咯烷酮溶于50.0g去离子水中，物理混合分散均匀后，加入50.0g镍钴锰三元材料，搅拌40min，得到三元材料分散液；(1) 0.067 g of graphene is dispersed in an organic solvent, ultrasonically dispersed for 40 min to obtain a graphene dispersion, and then a weight ratio of 0.133 g of carbon nanotubes, and a small amount of a silane coupling agent are added to the solution, and stirred for 30 minutes. The coupled graphene-carbon nanotube dispersion liquid is obtained; 1.0 g of polyvinylpyrrolidone is dissolved in 50.0 g of deionized water at normal temperature, and after physical mixing and dispersion, 50.0 g of nickel-cobalt-manganese ternary material is added and stirred for 40 minutes. Ternary material dispersion;
(2)将偶联的石墨烯-碳纳米管分散液倒入三元材料分散液中，分散10min后，置于恒温搅拌器中，60℃低温搅拌蒸发掉溶剂；(2) Pour the coupled graphene-carbon nanotube dispersion into the ternary material dispersion, disperse for 10 minutes, place in a constant temperature stirrer, and evaporate the solvent at 60 ° C under low temperature stirring;
(3)将上述产物研磨后，400目过筛，后置于氮气气氛中烧结，以2℃/min升温至300℃，并保温5小时。自然冷却后，研磨后400目过筛得到偶联的碳纳米管-石墨烯复合三维网络结构包覆的三元材料。(3) After grinding the above product, 400 mesh was sieved, and then sintered in a nitrogen atmosphere, and heated to 300 ° C at 2 ° C / min, and kept for 5 hours. After natural cooling, 400 mesh was sieved after grinding to obtain a ternary material coated with a coupled carbon nanotube-graphene composite three-dimensional network structure.
实施例7：Example 7
本实施方式与实施例6不同的是步骤二中所选用的蒸发溶剂的温度。具体制备方法如下：This embodiment differs from Example 6 in the temperature of the evaporating solvent selected in the second step. The specific preparation method is as follows:
将步骤一中所得的样品，即将偶联的石墨烯-碳纳米管分散液倒入三元材料分散液中，分散10min后，置于恒温搅拌器中，70℃低温搅拌蒸发掉溶剂；The sample obtained in the first step, that is, the coupled graphene-carbon nanotube dispersion liquid is poured into the ternary material dispersion liquid, dispersed for 10 minutes, placed in a constant temperature stirrer, and the solvent is evaporated at a low temperature of 70 ° C;
其他步骤与实施例6相同，得到本发明中的正极材料，即Gs-CNTs(12)@LNCM。The other steps were the same as in Example 6, and the positive electrode material of the present invention, that is, Gs-CNTs (12) @ LNCM was obtained.
实施例8：Example 8
(1)将0.067g的石墨烯分散在有机溶剂中，超声分散40min得到石墨烯分散液，然后向溶液中加入重量比为0.133g的碳纳米管，以及少量的硅烷偶联剂，搅拌30min，得到偶联的石墨烯-碳纳米管分散液；常温下，将1.0g聚乙烯吡咯烷酮溶于50.0g去离子水中，物理混合分散均匀后，加入50.0g镍钴锰三元材料，搅拌40min，得到三元材料分散液；(1) 0.067 g of graphene is dispersed in an organic solvent, ultrasonically dispersed for 40 min to obtain a graphene dispersion, and then a weight ratio of 0.133 g of carbon nanotubes, and a small amount of a silane coupling agent are added to the solution, and stirred for 30 minutes. The coupled graphene-carbon nanotube dispersion liquid is obtained; 1.0 g of polyvinylpyrrolidone is dissolved in 50.0 g of deionized water at normal temperature, and after physical mixing and dispersion, 50.0 g of nickel-cobalt-manganese ternary material is added and stirred for 40 minutes. Ternary material dispersion;
(2)将偶联的石墨烯-碳纳米管分散液倒入三元材料分散液中，分散10min后，置于恒温搅拌器中，80℃低温搅拌蒸发掉溶剂；(2) Pour the coupled graphene-carbon nanotube dispersion into the ternary material dispersion, disperse for 10 min, place in a constant temperature stirrer, and evaporate the solvent at a low temperature of 80 ° C;
(3)将上述产物研磨后，400目过筛，后置于氮气气氛中烧结，以2℃/min升温至250℃，并保温5小时。自然冷却后，研磨后400目过筛得到偶联的碳纳米管-石墨烯复合三维网络结构包覆的三元材料。(3) After grinding the above product, it was sieved at 400 mesh, then sintered in a nitrogen atmosphere, heated to 250 ° C at 2 ° C / min, and kept for 5 hours. After natural cooling, 400 mesh was sieved after grinding to obtain a ternary material coated with a coupled carbon nanotube-graphene composite three-dimensional network structure.
实施例9：Example 9
本实施方式与实施例8不同的是步骤三种材料的煅烧温度。具体制备方法如下：This embodiment differs from Example 8 in the calcination temperature of the three materials in the step. The specific preparation method is as follows:
将步骤二中所得的产物研磨后，400目过筛，后置于氮气气氛中烧结，以2℃/min升温至400℃，并保温5小时。自然冷却后，研磨后400目过筛得到偶联的碳纳米管-石墨烯复合三维网络结构包覆的三元材料。After the product obtained in the second step was ground, sieved through 400 mesh, and then sintered in a nitrogen atmosphere, and heated to 400 ° C at 2 ° C / min, and kept for 5 hours. After natural cooling, 400 mesh was sieved after grinding to obtain a ternary material coated with a coupled carbon nanotube-graphene composite three-dimensional network structure.
其他与实施例8相同，得到本发明中的正极材料。Otherwise in the same manner as in Example 8, the positive electrode material of the present invention was obtained.
实施例10： Example 10:
本实施方式与实施例8不同的是步骤三中材料的煅烧温度。具体制备方法如下：The difference between this embodiment and the embodiment 8 is the calcination temperature of the material in the third step. The specific preparation method is as follows:
将步骤二中所得的产物研磨后，400目过筛，后置于氮气气氛中烧结，以2℃/min升温至500℃，并保温5小时。自然冷却后，研磨后400目过筛得到偶联的碳纳米管-石墨烯复合三维网络结构包覆的三元材料。After the product obtained in the second step was ground, 400 mesh was sieved, and then sintered in a nitrogen atmosphere, and heated to 500 ° C at 2 ° C / min, and kept for 5 hours. After natural cooling, 400 mesh was sieved after grinding to obtain a ternary material coated with a coupled carbon nanotube-graphene composite three-dimensional network structure.
其他与实施例8相同，得到本发明中的正极材料。Otherwise in the same manner as in Example 8, the positive electrode material of the present invention was obtained.
实施例11：Example 11
(1)将0.067g的石墨烯分散在有机溶剂中，超声分散40min得到石墨烯分散液，然后向溶液中加入重量比为0.133g的碳纳米管，以及少量的硅烷偶联剂，搅拌30min，得到偶联的石墨烯-碳纳米管分散液；常温下，将1.0g聚乙烯吡咯烷酮溶于50.0g去离子水中，物理混合分散均匀后，加入50.0g镍钴锰三元材料，搅拌40min，得到三元材料分散液；(1) 0.067 g of graphene is dispersed in an organic solvent, ultrasonically dispersed for 40 min to obtain a graphene dispersion, and then a weight ratio of 0.133 g of carbon nanotubes, and a small amount of a silane coupling agent are added to the solution, and stirred for 30 minutes. The coupled graphene-carbon nanotube dispersion liquid is obtained; 1.0 g of polyvinylpyrrolidone is dissolved in 50.0 g of deionized water at normal temperature, and after physical mixing and dispersion, 50.0 g of nickel-cobalt-manganese ternary material is added and stirred for 40 minutes. Ternary material dispersion;
(2)将偶联的石墨烯-碳纳米管分散液倒入三元材料分散液中，分散10min后，置于恒温搅拌器中，80℃低温搅拌蒸发掉溶剂；(2) Pour the coupled graphene-carbon nanotube dispersion into the ternary material dispersion, disperse for 10 min, place in a constant temperature stirrer, and evaporate the solvent at a low temperature of 80 ° C;
(3)将上述产物研磨后，400目过筛，后置于氮气气氛中烧结，以2℃/min升温至300℃，并保温3小时。自然冷却后，研磨后400目过筛得到偶联的碳纳米管-石墨烯复合三维网络结构包覆的三元材料。(3) After grinding the above product, 400 mesh was sieved, and then sintered in a nitrogen atmosphere, and heated to 300 ° C at 2 ° C / min, and kept for 3 hours. After natural cooling, 400 mesh was sieved after grinding to obtain a ternary material coated with a coupled carbon nanotube-graphene composite three-dimensional network structure.
实施例12：Example 12
本实施方式与实施例11不同的是步骤三中材料的煅烧时间。具体制备方法如下：The difference between this embodiment and the embodiment 11 is the calcination time of the material in the third step. The specific preparation method is as follows:
将步骤二中所得的产物研磨后，经400目过筛后，置于氮气气氛中烧结，以2℃/min升温至300℃，并保温4小时。自然冷却后，研磨后400目过筛得到偶联的碳纳米管-石墨烯复合三维网络结构包覆的三元材料。The product obtained in the second step was ground, sieved through 400 mesh, sintered in a nitrogen atmosphere, heated to 300 ° C at 2 ° C / min, and kept for 4 hours. After natural cooling, 400 mesh was sieved after grinding to obtain a ternary material coated with a coupled carbon nanotube-graphene composite three-dimensional network structure.
其他步骤与实施例11相同，得到本发明中的正极材料。The other steps were the same as in Example 11 to obtain a positive electrode material in the present invention.
实施例13：Example 13
本实施方式与实施例11不同的是步骤三中材料的煅烧时间。具体制备方法如下：The difference between this embodiment and the embodiment 11 is the calcination time of the material in the third step. The specific preparation method is as follows:
将步骤二中所得的产物研磨后，经400目过筛后，置于氮气气氛中烧结，以2℃/min升温至300℃，并保温6小时。自然冷却后，研磨后400目过筛得到偶联的碳纳米管-石墨烯复合三维网络结构包覆的三元材料。The product obtained in the second step was ground, sieved through 400 mesh, sintered in a nitrogen atmosphere, and heated to 300 ° C at 2 ° C / min, and kept for 6 hours. After natural cooling, 400 mesh was sieved after grinding to obtain a ternary material coated with a coupled carbon nanotube-graphene composite three-dimensional network structure.
其他步骤与实施例11相同，得到本发明中的正极材料。The other steps were the same as in Example 11 to obtain a positive electrode material in the present invention.
实施例14：Example 14
本实施方式与实施例1不同的是步骤一中石墨烯-碳纳米管的包覆量。实施例1中石墨烯-碳纳米管的包覆量为0.4％。This embodiment differs from Example 1 in the amount of coating of graphene-carbon nanotubes in the first step. The coating amount of graphene-carbon nanotubes in Example 1 was 0.4%.
将0.05g的石墨烯分散在有机溶剂中，超声分散40min得到石墨烯分散液，然后向溶液中加入重量比为0.05g的碳纳米管，以及少量的硅烷偶联剂，搅拌30min，得到偶联的石墨烯-碳纳米管分散液；常温下，将1.0g聚乙烯吡咯烷酮溶于50.0g去离子水中，物理混合分散均匀后，加入50.0g镍钴锰三元材料，搅拌40min，得到三元材料分散液； 0.05 g of graphene was dispersed in an organic solvent, ultrasonically dispersed for 40 min to obtain a graphene dispersion, and then a weight ratio of 0.05 g of carbon nanotubes was added to the solution, and a small amount of a silane coupling agent was stirred for 30 minutes to obtain a coupling. Graphene-carbon nanotube dispersion; 1.0 g of polyvinylpyrrolidone is dissolved in 50.0 g of deionized water at normal temperature, and after physical mixing and dispersion, 50.0 g of nickel-cobalt-manganese ternary material is added and stirred for 40 minutes to obtain a ternary material. Dispersions;
其他步骤与实施例1相同，得到本发明中的正极材料。石墨烯-碳纳米管的包覆量为0.2％。The other steps were the same as in Example 1, and the positive electrode material in the present invention was obtained. The coating amount of graphene-carbon nanotubes was 0.2%.
实施例15：Example 15
本实施方式与实施例1不同的是步骤一中石墨烯-碳纳米管的包覆量。实施例1中石墨烯-碳纳米管的包覆量为0.4％。This embodiment differs from Example 1 in the amount of coating of graphene-carbon nanotubes in the first step. The coating amount of graphene-carbon nanotubes in Example 1 was 0.4%.
将0.075g的石墨烯分散在有机溶剂中，超声分散40min得到石墨烯分散液，然后向溶液中加入重量比为0.075g的碳纳米管，以及少量的硅烷偶联剂，搅拌30min，得到偶联的石墨烯-碳纳米管分散液；常温下，将1.0g聚乙烯吡咯烷酮溶于50.0g去离子水中，物理混合分散均匀后，加入50.0g镍钴锰三元材料，搅拌40min，得到三元材料分散液；0.075 g of graphene was dispersed in an organic solvent, ultrasonically dispersed for 40 min to obtain a graphene dispersion, and then a weight ratio of 0.075 g of carbon nanotubes was added to the solution, and a small amount of a silane coupling agent was stirred for 30 minutes to obtain a coupling. Graphene-carbon nanotube dispersion; 1.0 g of polyvinylpyrrolidone is dissolved in 50.0 g of deionized water at normal temperature, and after physical mixing and dispersion, 50.0 g of nickel-cobalt-manganese ternary material is added and stirred for 40 minutes to obtain a ternary material. Dispersions;
其他步骤与实施例1相同，得到本发明中的正极材料。石墨烯-碳纳米管的包覆量为0.3％。The other steps were the same as in Example 1, and the positive electrode material in the present invention was obtained. The coating amount of graphene-carbon nanotubes was 0.3%.
实施例16：Example 16:
本实施方式与实施例1不同的是步骤一中石墨烯-碳纳米管的包覆量。实施例1中石墨烯-碳纳米管的包覆量为0.4％。This embodiment differs from Example 1 in the amount of coating of graphene-carbon nanotubes in the first step. The coating amount of graphene-carbon nanotubes in Example 1 was 0.4%.
将0.25g的石墨烯分散在有机溶剂中，超声分散40min得到石墨烯分散液，然后向溶液中加入重量比为0.25g的碳纳米管，以及少量的硅烷偶联剂，搅拌30min，得到偶联的石墨烯-碳纳米管分散液；常温下，将1.0g聚乙烯吡咯烷酮溶于50.0g去离子水中，物理混合分散均匀后，加入50.0g镍钴锰三元材料，搅拌40min，得到三元材料分散液；0.25 g of graphene was dispersed in an organic solvent, ultrasonically dispersed for 40 min to obtain a graphene dispersion, and then a weight ratio of 0.25 g of carbon nanotubes was added to the solution, and a small amount of a silane coupling agent was stirred for 30 minutes to obtain a coupling. Graphene-carbon nanotube dispersion; 1.0 g of polyvinylpyrrolidone is dissolved in 50.0 g of deionized water at normal temperature, and after physical mixing and dispersion, 50.0 g of nickel-cobalt-manganese ternary material is added and stirred for 40 minutes to obtain a ternary material. Dispersions;
其他步骤与实施例1相同，得到本发明中的正极材料。石墨烯-碳纳米管的包覆量为1.0％。The other steps were the same as in Example 1, and the positive electrode material in the present invention was obtained. The coating amount of graphene-carbon nanotubes was 1.0%.
由实施例1、实施例13、实施例14、实施例15所制备的偶联的石墨烯-碳纳米管复合镍钴锰三元材料的倍率性能图如图1所示。The rate performance of the coupled graphene-carbon nanotube composite nickel cobalt manganese ternary material prepared in Example 1, Example 13, Example 14, and Example 15 is shown in FIG.
尽管上面结合图对本发明进行了描述，但是本发明并不局限于上述的具体实施方式，上述的具体实施方式仅仅是示意性的，而不是限制性的，本领域的普通技术人员在本发明的启示下，在不脱离本发明宗旨的情况下，还可以对上述实施方式进行变更和修改，这些均属于本发明的保护之内。 Although the present invention has been described in connection with the drawings, the present invention is not limited to the specific embodiments described above, and the specific embodiments described above are merely illustrative and not restrictive, and those of ordinary skill in the art It is to be understood that changes and modifications may be made to the above-described embodiments without departing from the spirit and scope of the invention.

Claims (7)

  1. 一种偶联的碳纳米管-石墨烯复合三维网络结构包覆的三元材料，以镍钴锰三元材料、碳纳米管和石墨烯为原料，其特征在于：以聚乙烯吡咯烷酮为分散剂，同时通过液相自组合的方式采用硅烷偶联剂来连接石墨烯和碳纳米管，使其形成三维网络结构，然后将偶联的碳纳米管-石墨烯复合材料和镍钴锰三元材料通过物理方法分散均匀后，包覆在镍钴锰三元材料的表面，置于惰性气氛中烧结得到均匀包覆的产品。A coupled carbon nanotube-graphene composite three-dimensional network structure coated ternary material, using nickel-cobalt-manganese ternary material, carbon nanotubes and graphene as raw materials, characterized in that polyvinylpyrrolidone is used as a dispersing agent At the same time, the silane coupling agent is used to connect the graphene and the carbon nanotubes by a liquid phase self-combination method to form a three-dimensional network structure, and then the coupled carbon nanotube-graphene composite material and the nickel cobalt manganese ternary material are formed. After being uniformly dispersed by a physical method, it is coated on the surface of the nickel-cobalt-manganese ternary material, and is sintered in an inert atmosphere to obtain a uniformly coated product.
  2. 根据权利要求1所述的三元材料的制备方法，其特征为，包括如下步骤：(1)常温下，将重量比为0.1-1％的石墨烯分散在有机溶剂中，超声分散40min得到石墨烯分散液，然后想溶液中加入重量比为0.2-0.8％的碳纳米管以及少量的硅烷偶联剂，搅拌30min得到偶联的石墨烯-碳纳米管分散液；(2)常温下，将重量比为2％的聚乙烯吡咯烷酮溶于去离子水中，物理混合分散均匀后，加入镍钴锰三元材料，搅拌40min得到三元材料分散液；(3)将上述偶联的石墨烯-碳纳米管分散液导入三元材料分散液中，分散10min后，置于恒温搅拌器中，60-80℃下搅拌蒸发掉溶剂；(4)将蒸发溶剂后的产物研磨后，400目过筛，然后置于保护气氛中于250-500℃下烧结3-6h，研磨过筛后得到产品。The method for preparing a ternary material according to claim 1, comprising the steps of: (1) dispersing graphene in a weight ratio of 0.1 to 1% in an organic solvent at room temperature, and dispersing the graphite for 40 minutes to obtain graphite. The olefin dispersion, then adding a weight ratio of 0.2-0.8% carbon nanotubes and a small amount of silane coupling agent to the solution, stirring for 30 minutes to obtain a coupled graphene-carbon nanotube dispersion; (2) at room temperature, The polyvinylpyrrolidone with a weight ratio of 2% is dissolved in deionized water, physically mixed and dispersed uniformly, then a nickel-cobalt-manganese ternary material is added, and stirred for 40 minutes to obtain a ternary material dispersion; (3) the above-mentioned coupled graphene-carbon The nanotube dispersion is introduced into the ternary material dispersion, dispersed for 10 minutes, placed in a constant temperature stirrer, and the solvent is evaporated under stirring at 60-80 ° C; (4) the product after evaporation of the solvent is ground, 400 mesh is sieved, Then, it is sintered in a protective atmosphere at 250-500 ° C for 3-6 h, and sieved to obtain a product.
  3. 根据权利要求2所述的三元材料的制备方法，其特征在于：所述石墨烯的比表面积为500-1000m2/g，其纳米片层数为2-6层；碳纳米管的比表面积为40-70m2/g，其粒径为60-100nm；石墨烯与碳纳米管的质量比为1:1-5。The method for preparing a ternary material according to claim 2, wherein the graphene has a specific surface area of 500-1000 m 2 /g, and the number of nanosheet layers is 2-6 layers; a specific surface area of the carbon nanotubes It is 40-70 m 2 /g, and its particle diameter is 60-100 nm; the mass ratio of graphene to carbon nanotubes is 1:1-5.
  4. 根据权利要求2所述的三元材料的制备方法，其特征在于：所述步骤(1)中，石墨烯的重量比为0.1-0.5％，碳纳米管的重量比为0.2-0.5％。The method for preparing a ternary material according to claim 2, wherein in the step (1), the weight ratio of the graphene is 0.1-0.5%, and the weight ratio of the carbon nanotubes is 0.2-0.5%.
  5. 根据权利要求2苏搜狐的三元材料的制备方法，其特征在于：步骤(1)中，有机溶剂为乙醇、异丙醇、正丁醇、丙三醇、甲醇、N-甲基吡咯烷酮和丙酮中的一种或两种。A method for preparing a ternary material of Su Sohu according to claim 2, wherein in the step (1), the organic solvent is ethanol, isopropanol, n-butanol, glycerol, methanol, N-methylpyrrolidone and acetone. One or two of them.
  6. 根据权利要求2所述的三元材料的制备方法，其特征在于：步骤(2)中，物理混合方式为搅拌、超声和高速剪切乳化中的一种或多种。The method for preparing a ternary material according to claim 2, wherein in the step (2), the physical mixing mode is one or more of stirring, ultrasonication, and high-speed shear emulsification.
  7. 根据权利要求1所述的三元材料的制备方法，其特征在于：步骤(4)中，保护气氛为氮气气氛或氩气气氛。 The method for preparing a ternary material according to claim 1, wherein in the step (4), the protective atmosphere is a nitrogen atmosphere or an argon atmosphere.
PCT/CN2016/085323 2015-07-09 2016-06-08 Ternary material coated with three-dimensional network structure of coupled carbon nanotube-graphene composite and manufacturing method thereof WO2017005078A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510399894.0 2015-07-09
CN201510399894.0A CN105070888B (en) 2015-07-09 2015-07-09 Ternary material of CNT graphene complex three-dimensional network structure cladding of coupling and preparation method thereof

Publications (1)

Publication Number Publication Date
WO2017005078A1 true WO2017005078A1 (en) 2017-01-12

Family

ID=54500207

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/085323 WO2017005078A1 (en) 2015-07-09 2016-06-08 Ternary material coated with three-dimensional network structure of coupled carbon nanotube-graphene composite and manufacturing method thereof

Country Status (2)

Country Link
CN (1) CN105070888B (en)
WO (1) WO2017005078A1 (en)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110885079A (en) * 2018-09-11 2020-03-17 天津大学 Preparation method of novel graphene-carbon nanotube composite material
CN111195584A (en) * 2018-11-16 2020-05-26 北京赛菲斯技术有限公司 Part surface modification method
CN111785965A (en) * 2020-05-22 2020-10-16 浙江兴海能源科技有限公司 Nanoscale graphene material dispersing process
CN112635732A (en) * 2020-12-17 2021-04-09 中国电子科技集团公司第十八研究所 Preparation method of graphene/lithium cobaltate composite positive electrode material
CN112886015A (en) * 2021-02-02 2021-06-01 广东凯金新能源科技股份有限公司 Three-dimensional carbon-silicon composite material and preparation method thereof
CN112892528A (en) * 2019-11-18 2021-06-04 国家纳米科学中心 Noble metal/carbon nano composite catalyst, preparation method and application thereof
CN113097461A (en) * 2021-03-29 2021-07-09 清华大学 Ternary cathode material @ yttrium oxide core-shell structure composite material and preparation method thereof
CN113130846A (en) * 2021-04-26 2021-07-16 南昌工程学院 Secondary battery anode material and battery thereof
CN113133297A (en) * 2021-04-20 2021-07-16 合肥工业大学 Super-crosslinked polystyrene based composite carbon aerogel electromagnetic shielding material and preparation method thereof
CN113488634A (en) * 2021-07-29 2021-10-08 浙江帕瓦新能源股份有限公司 Double-layer coated modified high-nickel cobalt-free single crystal ternary positive electrode material and preparation method thereof
CN113690428A (en) * 2021-08-24 2021-11-23 北京化工大学 SiO (silicon dioxide)xCarbon nanotube/graphene composite membrane and preparation method thereof
CN113921785A (en) * 2021-09-29 2022-01-11 陕西红马科技有限公司 Preparation method of three-dimensional mesh carbon coating ternary cathode material
CN113921789A (en) * 2021-10-08 2022-01-11 合肥国轩高科动力能源有限公司 Preparation method of carbon quantum dot modified NCM ternary cathode material and prepared NCM ternary cathode material
CN114142080A (en) * 2021-11-25 2022-03-04 深圳市瀚海龙科技有限公司 Ultra-capacity graphene battery and preparation method thereof
CN114275826A (en) * 2021-12-14 2022-04-05 湖北容百锂电材料有限公司 Graphene carbon surface modified nickel cobalt lithium manganate ternary positive electrode material and preparation method thereof
CN114447302A (en) * 2022-01-27 2022-05-06 中国科学院电工研究所 Layered oxide/conductive agent composite material and preparation method and application thereof
CN114512662A (en) * 2022-03-02 2022-05-17 芜湖天弋能源科技有限公司 Lithium ion battery anode material and preparation method thereof, and lithium ion battery
CN114639820A (en) * 2022-03-10 2022-06-17 陕西沣锡致远新材料科技有限公司 Preparation method of spherical glucose nickel-cobalt-manganese complex and application of spherical glucose nickel-cobalt-manganese complex to secondary battery
CN115124088A (en) * 2021-03-29 2022-09-30 天目湖先进储能技术研究院有限公司 Composite inorganic lithium salt coated positive electrode material and preparation method and application thereof
CN116344781A (en) * 2023-05-26 2023-06-27 四川新能源汽车创新中心有限公司 Method for coating halide electrolyte on surface of electrode active material and active material

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105070888B (en) * 2015-07-09 2017-11-14 山东玉皇新能源科技有限公司 Ternary material of CNT graphene complex three-dimensional network structure cladding of coupling and preparation method thereof
CN105702926B (en) * 2016-02-01 2018-07-06 浙江天能能源科技股份有限公司 A kind of three-dimensional net structure ternary composite cathode material and preparation method thereof
GB201604341D0 (en) * 2016-03-14 2016-04-27 Aurubis Belgium Nv Sa Composition
CN105839000A (en) * 2016-05-23 2016-08-10 安徽鑫宏机械有限公司 Casting method of slurry valve body for papermaking
CN106450277A (en) * 2016-11-01 2017-02-22 江苏海四达电源股份有限公司 Electrode system used in low-temperature rate type lithium ion battery
CN106374097A (en) * 2016-12-02 2017-02-01 东莞市创明电池技术有限公司 Preparation method of surface-controlled PANI-g-CNTs and NCM (Polyaniline-grafted-Carbon Nano Tubes and Nickel-Cobalt-Manganese) electrode material for lithium battery
US11108037B2 (en) 2016-12-30 2021-08-31 Beijing Tunghsu Carbon Advanced Materials Technology Co., Ltd. Method for preparing graphene/ternary material composite for use in lithium ion batteries and product thereof
CN106784748B (en) * 2017-03-21 2018-01-26 宝汽宏泰新能源有限公司 A kind of silicon substrate nickel cobalt manganese lithium ternary electrode material of lithium battery and preparation method thereof
CN106992286B (en) * 2017-03-24 2019-08-13 江苏乐能电池股份有限公司 A kind of preparation method of high capacity trielement composite material
TWI682578B (en) 2017-12-12 2020-01-11 財團法人工業技術研究院 Positive electrode plate and method of forming slurry for positive electrode plate
CN108390011B (en) * 2018-03-08 2020-04-07 南京师范大学 Lithium manganate, graphene oxide and carbon nanotube composite aerogel as well as preparation method and application thereof
CN109390576A (en) * 2018-12-05 2019-02-26 长沙矿冶研究院有限责任公司 A kind of preparation method of the nickelic tertiary cathode material of carbon coating
CN109728264B (en) * 2018-12-06 2021-03-30 复旦大学 Composite film of carbon-based frame loaded nanosheet assembled hollow open microspheres and preparation method and application thereof
CN109873148A (en) * 2019-03-06 2019-06-11 昆明理工大学 The preparation method of the modified nickelic ternary lithium battery composite positive pole of conducting polymer base
CN110459759B (en) * 2019-08-19 2020-10-20 湖南金富力新能源股份有限公司 Lithium ion battery anode material prepared by using rotary device and preparation method and application thereof
CN112436139A (en) * 2019-08-24 2021-03-02 深圳格林德能源集团有限公司 Preparation method of three-dimensional composite conductive agent
TWI759002B (en) 2019-12-09 2022-03-21 財團法人工業技術研究院 Positive electrode material, positive electrode and battery employing the same
CN111151765B (en) * 2020-01-20 2023-02-03 西安稀有金属材料研究院有限公司 Preparation method of three-dimensional structure nano carbon material reinforced copper-based composite material
CN111793247B (en) * 2020-07-24 2022-02-08 江苏清大际光新材料有限公司 Carbon material and preparation method and application thereof
CN111952585A (en) * 2020-08-18 2020-11-17 光鼎铷业(广州)集团有限公司 High-compaction-density rubidium-doped lithium battery positive electrode material and preparation method thereof
CN112186158A (en) * 2020-09-28 2021-01-05 蜂巢能源科技有限公司 Positive electrode composite material and preparation method and application thereof
CN112259724A (en) * 2020-10-30 2021-01-22 蜂巢能源科技有限公司 Composite positive electrode material, preparation method thereof, lithium battery positive electrode material and lithium battery
CN112993249A (en) * 2021-05-12 2021-06-18 蜂巢能源科技有限公司 Graphene composite positive electrode material, preparation method thereof and lithium ion battery
CN113737512B (en) * 2021-09-15 2023-08-08 武汉纺织大学 Method for preparing elastic conductive fiber by micro-fluid coating technology and elastic conductive fiber
CN114899397B (en) * 2022-03-24 2023-01-31 楚能新能源股份有限公司 Lithium ion battery anode material and preparation method of secondary battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104009239A (en) * 2013-12-16 2014-08-27 青岛乾运高科新材料股份有限公司 Nano carbon doped manganese-based solid solution anode material and preparation method thereof
US20140332731A1 (en) * 2012-04-02 2014-11-13 CNano Technology Limited Electrode Composition for Battery
CN104157854A (en) * 2014-07-31 2014-11-19 山东玉皇新能源科技有限公司 Preparation method for ternary positive electrode material of graphene composite lithium ion battery
CN105070888A (en) * 2015-07-09 2015-11-18 山东玉皇新能源科技有限公司 Coupled carbon nano tube-graphene composite three-dimensional network structure-coated ternary material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103725263A (en) * 2013-12-17 2014-04-16 张家港康得新光电材料有限公司 Film made from graphene-carbon nanotube composite material and preparation method of film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140332731A1 (en) * 2012-04-02 2014-11-13 CNano Technology Limited Electrode Composition for Battery
CN104009239A (en) * 2013-12-16 2014-08-27 青岛乾运高科新材料股份有限公司 Nano carbon doped manganese-based solid solution anode material and preparation method thereof
CN104157854A (en) * 2014-07-31 2014-11-19 山东玉皇新能源科技有限公司 Preparation method for ternary positive electrode material of graphene composite lithium ion battery
CN105070888A (en) * 2015-07-09 2015-11-18 山东玉皇新能源科技有限公司 Coupled carbon nano tube-graphene composite three-dimensional network structure-coated ternary material and preparation method thereof

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110885079A (en) * 2018-09-11 2020-03-17 天津大学 Preparation method of novel graphene-carbon nanotube composite material
CN111195584A (en) * 2018-11-16 2020-05-26 北京赛菲斯技术有限公司 Part surface modification method
CN112892528A (en) * 2019-11-18 2021-06-04 国家纳米科学中心 Noble metal/carbon nano composite catalyst, preparation method and application thereof
CN111785965A (en) * 2020-05-22 2020-10-16 浙江兴海能源科技有限公司 Nanoscale graphene material dispersing process
CN111785965B (en) * 2020-05-22 2024-02-13 浙江兴海能源科技有限公司 Nanometer graphene material dispersing process
CN112635732A (en) * 2020-12-17 2021-04-09 中国电子科技集团公司第十八研究所 Preparation method of graphene/lithium cobaltate composite positive electrode material
CN112886015A (en) * 2021-02-02 2021-06-01 广东凯金新能源科技股份有限公司 Three-dimensional carbon-silicon composite material and preparation method thereof
CN113097461B (en) * 2021-03-29 2022-03-29 清华大学 Ternary cathode material @ yttrium oxide core-shell structure composite material and preparation method thereof
CN115124088A (en) * 2021-03-29 2022-09-30 天目湖先进储能技术研究院有限公司 Composite inorganic lithium salt coated positive electrode material and preparation method and application thereof
CN113097461A (en) * 2021-03-29 2021-07-09 清华大学 Ternary cathode material @ yttrium oxide core-shell structure composite material and preparation method thereof
CN115124088B (en) * 2021-03-29 2023-10-20 天目湖先进储能技术研究院有限公司 Composite inorganic lithium salt coated positive electrode material and preparation method and application thereof
CN113133297A (en) * 2021-04-20 2021-07-16 合肥工业大学 Super-crosslinked polystyrene based composite carbon aerogel electromagnetic shielding material and preparation method thereof
CN113133297B (en) * 2021-04-20 2023-06-27 合肥工业大学 Super-crosslinked polystyrene-based composite carbon aerogel electromagnetic shielding material and preparation method thereof
CN113130846B (en) * 2021-04-26 2022-03-01 南昌工程学院 Secondary battery anode material and battery thereof
CN113130846A (en) * 2021-04-26 2021-07-16 南昌工程学院 Secondary battery anode material and battery thereof
CN113488634A (en) * 2021-07-29 2021-10-08 浙江帕瓦新能源股份有限公司 Double-layer coated modified high-nickel cobalt-free single crystal ternary positive electrode material and preparation method thereof
CN113690428A (en) * 2021-08-24 2021-11-23 北京化工大学 SiO (silicon dioxide)xCarbon nanotube/graphene composite membrane and preparation method thereof
CN113690428B (en) * 2021-08-24 2024-02-02 北京化工大学 SiO (silicon dioxide) x Carbon nano tube/graphene composite film and preparation method thereof
CN113921785A (en) * 2021-09-29 2022-01-11 陕西红马科技有限公司 Preparation method of three-dimensional mesh carbon coating ternary cathode material
CN113921789A (en) * 2021-10-08 2022-01-11 合肥国轩高科动力能源有限公司 Preparation method of carbon quantum dot modified NCM ternary cathode material and prepared NCM ternary cathode material
CN114142080A (en) * 2021-11-25 2022-03-04 深圳市瀚海龙科技有限公司 Ultra-capacity graphene battery and preparation method thereof
CN114142080B (en) * 2021-11-25 2024-04-05 东莞市茂盛新能源科技有限公司 Super-capacity graphene battery and preparation method thereof
CN114275826B (en) * 2021-12-14 2023-02-28 湖北容百锂电材料有限公司 Graphene carbon surface modified nickel cobalt lithium manganate ternary positive electrode material and preparation method thereof
CN114275826A (en) * 2021-12-14 2022-04-05 湖北容百锂电材料有限公司 Graphene carbon surface modified nickel cobalt lithium manganate ternary positive electrode material and preparation method thereof
CN114447302A (en) * 2022-01-27 2022-05-06 中国科学院电工研究所 Layered oxide/conductive agent composite material and preparation method and application thereof
CN114447302B (en) * 2022-01-27 2024-02-13 中国科学院电工研究所 Layered oxide/conductive agent composite material and preparation method and application thereof
CN114512662A (en) * 2022-03-02 2022-05-17 芜湖天弋能源科技有限公司 Lithium ion battery anode material and preparation method thereof, and lithium ion battery
CN114639820A (en) * 2022-03-10 2022-06-17 陕西沣锡致远新材料科技有限公司 Preparation method of spherical glucose nickel-cobalt-manganese complex and application of spherical glucose nickel-cobalt-manganese complex to secondary battery
CN114639820B (en) * 2022-03-10 2024-02-27 陕西沣锡致远新材料科技有限公司 Preparation method of spherical glucose nickel cobalt manganese complex and application of spherical glucose nickel cobalt manganese complex in secondary battery
CN116344781A (en) * 2023-05-26 2023-06-27 四川新能源汽车创新中心有限公司 Method for coating halide electrolyte on surface of electrode active material and active material
CN116344781B (en) * 2023-05-26 2023-09-01 四川新能源汽车创新中心有限公司 Method for coating halide electrolyte on surface of electrode active material and active material

Also Published As

Publication number Publication date
CN105070888B (en) 2017-11-14
CN105070888A (en) 2015-11-18

Similar Documents

Publication Publication Date Title
WO2017005078A1 (en) Ternary material coated with three-dimensional network structure of coupled carbon nanotube-graphene composite and manufacturing method thereof
Sandhya et al. Lithium titanate as anode material for lithium-ion cells: a review
WO2018120147A1 (en) Method for preparing graphene/ternary material composite for use in lithium ion batteries and product thereof
WO2021108983A1 (en) Secondary battery, device, artificial graphite, and preparation method therefor
CN100427387C (en) Lithium ion battery positive material vanadium lithium phosphate sol gelatin preparation method
Gao et al. Self-doping Ti1-xNb2+ xO7 anode material for lithium-ion battery and its electrochemical performance
CN107482182B (en) Carbon-coated ion-doped manganese phosphate lithium electrode material and preparation method thereof
Idris et al. Effects of polypyrrole on the performance of nickel oxide anode materials for rechargeable lithium-ion batteries
CN103904335A (en) Lithium ion battery negative material structure and preparation method thereof
Chaudhary et al. Surface modification of cathode materials for energy storage devices: A review
Xia et al. Zn2SnO4-carbon cloth freestanding flexible anodes for high-performance lithium-ion batteries
Huang et al. Advanced Li-rich cathode collaborated with graphite/silicon anode for high performance Li-ion batteries in half and full cells
CN105226273B (en) A kind of iron manganese phosphate for lithium and preparation method and application
Li et al. TiO2-based ionogel electrolytes for lithium metal batteries
Cao et al. Sodium vanadate nanowires@ polypyrrole with synergetic core-shell structure for enhanced reversible sodium-ion storage
Kang et al. Design of Nb2O5@ rGO composites to optimize the lithium-ion storage performance
Wang et al. Synthesis and electrochemical performance of three-dimensional ordered hierarchically porous Li4Ti5O12 for high performance lithium ion batteries
Hu et al. Ultrasonic-assisted synthesis of LiFePO4/C composite for lithium-ion batteries using iron powder as the reactant
Cheng et al. Hydrothermal synthesis of LiNi0. 5Mn1. 5O4 sphere and its performance as high-voltage cathode material for lithium ion batteries
Liu et al. Investigation the electrochemical performance of layered cathode material Li1. 2Ni0. 2Mn0. 6O2 coated with Li4Ti5O12
Zhang et al. A review on electrode materials of fast‐charging lithium‐ion batteries
CN105742627A (en) Preparation method for LiNi<x>Co<y>Mn<1-x-y>Br<z>O<2-z>/graphene composite cathode material
Liu et al. Excellent high-rate capability of micron-sized Co-free α-Ni (OH) 2 for high-power Ni-MH battery
Yi et al. Li4Ti5O12-rutile TiO2 nanosheet composite as a high performance anode material for lithium-ion battery
Fu et al. Single crystalline nanorods of Na0. 44MnO2 enhanced by reduced graphene oxides as a high rate and high capacity cathode material for sodium-ion batteries

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16820729

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16820729

Country of ref document: EP

Kind code of ref document: A1