WO2015139660A1 - 多孔碳纳米管微球及其制备方法与应用、金属锂-骨架碳复合材料及其制备方法、负极和电池 - Google Patents

多孔碳纳米管微球及其制备方法与应用、金属锂-骨架碳复合材料及其制备方法、负极和电池 Download PDF

Info

Publication number
WO2015139660A1
WO2015139660A1 PCT/CN2015/074733 CN2015074733W WO2015139660A1 WO 2015139660 A1 WO2015139660 A1 WO 2015139660A1 CN 2015074733 W CN2015074733 W CN 2015074733W WO 2015139660 A1 WO2015139660 A1 WO 2015139660A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon nanotube
porous carbon
lithium
battery
metal
Prior art date
Application number
PCT/CN2015/074733
Other languages
English (en)
French (fr)
Inventor
王亚龙
杜兆龙
卢威
陈立桅
Original Assignee
中国科学院苏州纳米技术与纳米仿生研究所
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
Priority claimed from CN201410106376.0A external-priority patent/CN104925778B/zh
Priority claimed from CN201410395114.0A external-priority patent/CN105374991B/zh
Application filed by 中国科学院苏州纳米技术与纳米仿生研究所 filed Critical 中国科学院苏州纳米技术与纳米仿生研究所
Priority to EP15765300.7A priority Critical patent/EP3133047B8/en
Priority to KR1020167029453A priority patent/KR101900780B1/ko
Priority to US15/127,809 priority patent/US10868298B2/en
Priority to JP2016558783A priority patent/JP6445585B2/ja
Publication of WO2015139660A1 publication Critical patent/WO2015139660A1/zh

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
    • H01M4/362—Composites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • 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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
    • Y10S977/742—Carbon nanotubes, CNTs
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/84—Manufacture, treatment, or detection of nanostructure
    • Y10S977/842—Manufacture, treatment, or detection of nanostructure for carbon nanotubes or fullerenes
    • Y10S977/847—Surface modifications, e.g. functionalization, coating
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/902—Specified use of nanostructure
    • Y10S977/932—Specified use of nanostructure for electronic or optoelectronic application
    • Y10S977/948—Energy storage/generating using nanostructure, e.g. fuel cell, battery

Definitions

  • the present application relates to the field of materials science, and in particular to a porous carbon nanotube microsphere and a preparation method and application thereof.
  • the present application also relates to the field of energy batteries, and in particular to a metal lithium-skeletal carbon composite material, a preparation method thereof, a negative electrode and a battery.
  • Carbon nanotubes have good electrical conductivity and mechanical strength, in material reinforcement, field emission, The fields of drug delivery, nanoelectronics and nanodevices have broad application value and application prospects.
  • the carbon nanotubes themselves have good mechanical strength, while maintaining the advantages of the general microsphere structure.
  • the porous carbon nanotube microspheres have self-supporting ability, and the sphere maintains high mechanical strength, and can maintain the integrity of the granular structure without being damaged under a certain external pressure.
  • the porous carbon nanotube microspheres have a large number of controllable void structures, which improves the space volume utilization.
  • Porous carbon nanotube microspheres are also characterized by electrical conductivity and strong chemical stability, and their properties have been greatly improved on the basis of traditional carbon nanotube materials.
  • Porous carbon nanotube microspheres can accommodate a large number of guest molecules or large-sized objects, and can be used to carry a variety of functional materials to form composite functional materials, which has broad application prospects.
  • the template method and the micelle method use the template method and the micelle method, and it is difficult to obtain a large number of carbon nanotube microspheres for practical use.
  • the template method and the micelle method introduce substances such as surfactants to improve the affinity between the carbon nanotubes, which causes the carbon nanotubes to mainly form the outer shell of the sphere, and the carbon nanotubes formed in the sphere are too small to form carbon.
  • the nanotube microspheres are hollow structures and are difficult to serve as carrier materials for carrying guest materials.
  • lithium batteries have high energy density, good cycle performance, environmental friendliness, etc., and are widely used in transportation, communication, electronic equipment and other fields.
  • lithium-ion batteries generally use graphite materials as negative electrodes, and the theoretical capacity is 372 mAh/g, and the reversible capacity is generally about 340 mAh/g; while the specific capacity of metallic lithium is 3860 mAh/g, which is more than 10 times that of graphite negative electrodes.
  • the use of metallic lithium as a negative electrode for lithium ion batteries will greatly increase the energy density of lithium ion batteries.
  • lithium ions may be unevenly deposited on the metal lithium negative electrode during the charging process, and the dendrite piercing the separator may cause a short circuit and may cause the battery to burn or explode.
  • Metal lithium anodes have not been commercially available.
  • US FMC Company (Patent US 8,021,496 B2, US 2013/0181160 A1, CN102255080 A) prepares lithium metal particles of 20 ⁇ m to 100 ⁇ m by melt emulsification, and then the surface is modified to prepare an electrode sheet as a battery.
  • the use of the negative electrode can increase the specific surface area of the metallic lithium, reduce the effective surface current density of the negative electrode during charge and discharge, and alleviate the growth of dendrites.
  • Another object of the present invention is to provide a method for preparing a porous carbon nanotube microsphere material, which has the characteristics of simple operation, low cost, high production efficiency, and the like, and can realize large-scale production of porous carbon nanotube microsphere materials.
  • a porous carbon nanotube microsphere material which is a spherical or spheroidal particle composed of carbon nanotubes, and the inside of the particle is interlaced by carbon nanotubes to form a plurality of nanometer-scale pores, and the spherical or spheroidal particles have an average diameter of 1 ⁇ m. 100 ⁇ m.
  • the porous carbon nanotube microsphere material has at least any one of a microscopic spherical solid aggregate structure, a spherical aggregate structure, a spherical aggregate structure, a porous spherical aggregate structure, and a doughnut aggregate structure.
  • the preparation method of any one of the foregoing carbon nanotube microsphere materials comprises: dispersing the carbon nanotubes in a solvent to form a dispersion, and then spray-drying, thereby preparing the porous carbon nanotube microsphere material.
  • dispersion can be carried out without the aid of a surfactant.
  • the conditions for spray drying include an inlet air temperature of 150 to 250 ° C and an outlet temperature of 75 ° C or higher, for example, 75 to 150 ° C, but preferably an outlet temperature of 90 ° C or higher.
  • the specific steps of the preparation method may include: dispersing the carbon nanotubes in a solvent to obtain a dispersion, and then inputting the dispersion into the atomizer of the spray dryer, by controlling the inlet speed, the atomization condition, and the hot air temperature. And speed, the solvent in the droplets containing the carbon nanotubes is rapidly evaporated, thereby accumulating the carbon nanotubes in the liquid droplet to form porous carbon nanotube microspheres, and then the porous carbon nanotube microspheres are The bottom of the drying tower of the spray dryer and/or the cyclone is discharged.
  • the advantages of the present invention include: the inside of the porous carbon nanotube microsphere material is completely formed by the interlaced deposition of carbon nanotubes, and has a large number of nanometer-scale voids inside and outside the particle, and has a large
  • the pore size and good mechanical strength can be widely used in various fields as a carrier material for nanoscience, and the preparation method is simple, the controllability is strong, the cost is low, and the scale production is easy.
  • the preparation method of the present invention does not require the assistance of a surfactant, and completely forms a particle by interlacing carbon nanotubes with each other. Therefore, the particle has a large pore size and high mechanical strength, and is suitable for use as a loader.
  • Carrier material for bulk materials are examples of a surfactant, and completely forms a particle by interlacing carbon nanotubes with each other.
  • a A metal lithium-skeletal carbon composite material, a preparation method thereof, a negative electrode and a battery to overcome the deficiencies in the prior art.
  • the present invention provides the following technical solutions:
  • the embodiment of the present application discloses a metal-skeletal carbon composite material comprising a porous carbon material carrier and a metal formed in the pores of the carbon material carrier.
  • the metal comprises lithium, sodium and potassium.
  • the carbon material comprises carbon fiber microspheres, porous carbon nanotube microspheres, and acetylene black.
  • the porous carbon nanotube microspheres are the porous carbon nanotube microsphere materials in the first aspect of the invention.
  • the porous carbon nanotube microspheres have an average pore diameter of 10 nm to 50 nm.
  • the loading amount of metallic lithium in the metal-skeletal carbon composite material is from 5% by mass to 80% by mass, more preferably from 30 to 50% by mass.
  • the embodiment of the present application also discloses a battery negative electrode using the above metal lithium-skeletal carbon composite material.
  • the battery negative electrode of the present invention is a secondary battery negative electrode.
  • an embodiment of the present application further discloses a battery including the above negative electrode.
  • the battery of the present invention is a secondary battery.
  • the above secondary battery is a lithium-sulfur battery, a metal lithium-oxide battery, a metal lithium-polymer battery or a rechargeable lithium ion battery.
  • the embodiment of the present application further discloses a method for preparing a metal lithium-skeletal carbon composite material, which uniformly mixes metal lithium in a molten state with a porous carbon material carrier, and cools to obtain a metal lithium-skeletal carbon composite material.
  • the carbon material carrier is a porous carbon nanotube microsphere, and the porous carbon nanotube microsphere passes through the porous carbon nanotube micro of the first aspect.
  • the preparation method of the ball material is prepared.
  • the invention has the advantages that the metal lithium-skeletal carbon composite material prepared by the invention can be applied to various lithium batteries, and can be applied to metal lithium-oxide batteries, metal lithium-polymerization. Battery, rechargeable lithium-ion battery.
  • One area of noteworthy is the use of rechargeable lithium-ion batteries in portable electronic devices, and hybrid vehicles where secondary lithium batteries are expected to provide the highest specific capacity and good cycle performance while maintaining safety.
  • lithium metal as the most ideal negative
  • the polar material is not directly usable due to the occurrence of dendrites during charge and discharge, and therefore cannot be directly used.
  • the metal lithium-skeletal carbon composite prepared by the invention can inhibit dendrite formation, improve battery safety, and provide higher quality. Specific capacity and good cycle performance.
  • FIG. 1 is a schematic structural view of a porous carbon nanotube microsphere material preparation system according to an exemplary embodiment of the present invention, wherein: 1-air filter, 2-heater, 3-hot air distributor, 4-drying chamber, 5 - Filter, 6-pump, 7-centrifugal nozzle, 8-cyclone separator, 9-fan, 10-liquid tank.
  • 2a-2b are SEM images of the carboxylated carbon nanotube microspheres obtained in Example 1, and a comparison of the porosity of the carboxylated carbon nanotube microspheres and the unspherical carbon nanotubes. It can be seen from the curve obtained in Fig. 2b that when the carboxylated carbon nanotubes are converted into carboxylated carbon nanotube microspheres, the average pore volume of the carboxylated carbon nanotube microspheres is larger than that of the pure carboxylated carbon nanotubes.
  • Example 3 is a statistical diagram showing the particle size distribution of the carboxylated carbon nanotube microspheres prepared in Example 1 using a carboxy carbon tube dispersion having a concentration of 10 g/L.
  • 4a, 4b, 4c are SEM images of untreated porous multi-walled carbon nanotube microspheres obtained in Example 2, cross-sectional views of untreated porous multi-walled carbon nanotube microspheres, and untreated porous Comparison of porosity of multi-walled carbon nanotube microspheres and unspherical carbon nanotubes.
  • Figure 5 is a graph showing the particle size distribution of the porous multi-walled carbon nanotube microspheres obtained in Example 2 without any chemical treatment.
  • Example 6 is an SEM image of the hydroxylated multi-walled carbon nanotube microspheres obtained in Example 3.
  • 8a and 8b are respectively a first-stage charge and discharge curve and a battery cycle performance of the carbon-sulfur composite prepared in Example 4.
  • Example 10 is a charge and discharge curve of a carbon nanotube microsphere supercapacitor prepared in Example 5.
  • Figure 11 is a view showing the metal lithium-acetylene black composite material obtained in Example 7 of the present invention and lithium iron phosphate a battery charge and discharge cycle performance chart;
  • FIG. 12 is a scanning electron micrograph of a metal lithium-porous carbon nanotube microsphere composite prepared in Example 8 of the present invention, wherein the magnification of FIG. 12a (left) is 500 times, and FIG. 12b (right) is 10000 times;
  • Example 13 is an X-ray powder diffraction pattern of a metal lithium-porous carbon nanotube microsphere composite (upper part) and a porous carbon nanotube microsphere (bottom) obtained in Example 9 of the present invention, which contains a distinct metal lithium. Diffraction peak and a small amount of lithium nitride impurity peak;
  • Example 14 is a scanning electron micrograph of a porous carbon nanotube microsphere obtained in Example 10 of the present invention, the magnification of the left image is 500 times, and the right image is 10000 times;
  • Figure 15 is a timing chart showing a short circuit caused by dendrites in a battery composed of a metal lithium-porous carbon nanotube microsphere composite material and a lithium metal sheet obtained in Example 10 of the present invention, the battery being charged at a constant current of 0.2 mA (current density) 0.1 mA / cm 2 ) test the time of the short circuit caused by the dendrites, the comparative experiment is a battery composed of a metal lithium sheet and a metal lithium sheet;
  • Example 16 is a graph showing charge and discharge cycle performance of a simulated battery composed of a lithium metal-porous carbon nanotube microsphere composite material obtained in Example 10 of the present invention as a negative electrode and lithium spinel lithium manganate as a positive electrode;
  • Fig. 17 is a graph showing the charge and discharge cycle performance of a battery composed of a metal lithium-porous carbon nanotube microsphere composite material obtained in Example 10 of the present invention and lithium iron phosphate.
  • One aspect of the present invention provides a porous carbon nanotube microsphere material which is a spherical or spheroidal particle composed of carbon nanotubes, and the inside of the particle is interlaced by carbon nanotubes to form a plurality of nanoscale pores, the spherical or spheroidal
  • the particles have an average diameter of from 1 ⁇ m to 100 ⁇ m, preferably from 1 ⁇ m to 25 ⁇ m.
  • porous carbon nanotube microsphere material may have any one of a microscopic spherical solid aggregate structure, a spherical aggregate structure, a spherical aggregate structure, a porous spherical aggregate structure, and a doughnut aggregate structure, but is not limited thereto.
  • the carbon nanotubes may be selected from, but not limited to, multi-walled carbon nanotubes, double-walled carbon nanotubes, and A combination of any one or more of single-walled carbon nanotubes is preferably a multi-walled carbon nanotube.
  • the carbon nanotubes may be selected from one or more of commercially available carbon nanotubes, purified carbon nanotubes (purified carbon nanotubes without catalyst), and surface functionalized carbon nanotubes. Combination of species.
  • the group modified on the surface of the carbon nanotube may be selected from, but not limited to, a group such as -COOH, -OH, -NH 2 or the like.
  • the carbon nanotubes use pure carbon nanotubes without catalyst, especially pure multi-walled carbon nanotubes without catalyst.
  • the pressure can be up to 20 MPa by receiving a pressure test on the porous carbon nanotube microspheres.
  • the compressible pressure refers to a porous structure capable of retaining particles after the pressure is released.
  • the sphere is still not broken.
  • the specific surface area of the porous carbon nanotube microspheres was 100 to 1500 m 2 /g, preferably 150 to 500 m 2 /g.
  • the pores contained in the porous carbon nanotube microspheres have a pore size distribution of from 1 to 200 nm, preferably from 1 to 50 nm.
  • the carbon nanotube microspheres have a conductivity of 0.1 to 100 S.cm -1 , preferably 10 to 100 S.cm -1 , on the surface to be tested.
  • the present invention also provides a method for preparing a porous carbon nanotube microsphere, comprising: dissolving a carbon nanotube in a solvent to form a dispersion without the aid of a surfactant, and then spray drying to obtain the porous Carbon nanotube microspheres.
  • the carbon nanotube microsphere material of the present invention may have a form of powder or granules.
  • the preparation method may include dispersing carbon nanotubes in a solvent to obtain a surfactant-free dispersion in the liquid tank 10,
  • the dispersion is then fed into the centrifugal spray head 7 of the spray dryer via the filter 5 and the pump 6, and minute mist droplets are formed, and the mist droplets are placed in the spray dryer and by the air filter.
  • the hot air flow generated by the hot air flow of the heater 2 and the hot air distributor 3 is in parallel contact (where the instantaneous hot air flow temperature is the material inlet air temperature), and enters the drying tower 4 (when the material drying temperature is the material outlet temperature),
  • the solvent in the liquid mist is rapidly evaporated, and the carbon nanotubes in the liquid mist are aggregated to form carbon nanotube microspheres, and then the carbon nanotube microspheres are dried from the spray dryer.
  • the bottom of the column 4 and/or the cyclone 8 are collected and the hot air is drawn away by the fan 9.
  • the preparation method may include the following steps:
  • A dispersing the carbon nanotubes into a dispersion solvent (without a surfactant) by ultrasonic treatment to obtain a carbon nanotube dispersion
  • step B The dispersion obtained in step A is sprayed through the nozzle of the spray dryer at a certain speed, and the inlet air temperature and the outlet air temperature are preset, and the solution is kept in a stirring state during the spraying process, and is adjusted according to different types of spray dryers. Injection speed
  • the conditions of the spray drying include: the inlet air temperature is 150-250 ° C, and the outlet air temperature can be adjusted according to actual conditions, for example, 75 ° C or higher, such as 75-150 ° C, or 90 ° C or higher; a particularly preferred spray
  • the drying conditions include: the inlet air temperature is 190 to 210 ° C, and the outlet air temperature is 90 to 110 ° C.
  • the conditions of the spray drying may further preferably include a spraying speed of 1 ml/hr to 10000 liter/hr, preferably 1 ml/min to 100 liter/min, which is specifically adjusted according to the spray dryer model and specifications. .
  • the carbon nanometer may be selected from ordinary carbon nanotubes, carboxylated carbon nanotubes, hydroxylated carbon nanotubes, aminated carbon nanotubes, and the like.
  • the dispersion contains carbon nanotubes having a concentration of 10 to 50 g/L, and more preferably, the dispersion contains a concentration of 10 to 15 g/L.
  • the solvent is an organic and/or inorganic liquid capable of uniformly dispersing carbon nanotubes.
  • a combination of any one or more of water, ammonia water, hydrochloric acid solution, ethanol, acetone, and isopropyl alcohol is preferred.
  • the solvent may be a mixture of ethanol and water in a volume ratio of 1:10.
  • the spray dryer described in the present invention is a general term for a type of equipment which can spray a liquid material into a mist and quickly contact it with a high-temperature heat source environment to obtain a fixed shape and to be dried into a finished product. It is not limited to the structure shown in FIG. 1, and may be other devices having similar functions known in the art.
  • the inventor of the present invention creatively applies the conventional technique of spray drying to the preparation of porous carbon nanotube microspheres, in which the carbon nanotubes dispersed therein are subjected to droplet shrinkage during the evaporation of the droplets.
  • Agglomeration but after a certain degree of agglomeration, the carbon nanotube itself has good mechanical strength to prevent further compression, thereby obtaining a porous microsphere structure formed by interdigitating stacks of carbon nanotubes having a certain size and porosity.
  • the inside of the microspheres is filled with nanometer-sized voids.
  • the invention only makes The carbon nanotube microspheres can be obtained by spray drying with carbon nanotubes and a conventional dispersing solvent, which greatly simplifies the preparation process of the carbon nanotube microspheres, reduces the production cost, and obtains the particle size of the porous carbon nanotube microspheres.
  • Regular, dimensionally controllable, with good mechanical strength, electrical conductivity, porosity, can be widely used as an extension of carbon nanotubes in electrode materials, medical delivery and other fields.
  • porous carbon nanotube microspheres can be applied to the preparation of batteries, supercapacitors, and the like, for example, lithium sulfur battery electrodes, supercapacitor electrodes, and fuel cell electrodes.
  • an electrode material can be prepared from the aforementioned porous carbon nanotube microspheres.
  • the porous carbon nanotube microspheres are mixed with sulfur or the like to form a sulfur-carbon composite material in a manner known in the art, and then combined with carbon black, acetylene black, and other auxiliary materials such as excipients, binders, and the like.
  • the slurry is applied to a current collector such as an aluminum foil to form a positive electrode material applicable to a lithium sulfur battery, and then a primary or secondary lithium battery or the like can be formed by combining the positive electrode material with a negative electrode material, an electrolyte or the like.
  • the porous carbon nanotube microspheres may be combined with carbon black, acetylene black and other auxiliary materials, such as excipients, binders, etc., and then coated on a substrate such as aluminum foil.
  • the electrode sheet can then be formed by combining the electrode sheet with another electrode sheet, a separator, an electrolyte or the like.
  • a second aspect of the present application relates to a metal lithium-skeletal carbon composite material comprising a porous carbon material support and metallic lithium formed in the pores of the carbon material support.
  • the above carbon material skeleton structure may be a microsphere (average pore diameter of 10 to 50 nm) composed of a material such as carbon fiber or carbon nanotube, and acetylene black may also be used.
  • Other carbon skeleton materials having an average pore diameter in the range of 10 to 100 nm can also be selected as a carrier for absorbing molten lithium metal.
  • the mass proportion of metallic lithium in the metallic lithium-skeletal carbon composite is generally from 5% to 80%, more preferably from 30% to 50%.
  • the carbon material skeleton is prepared by spray drying using carbon nanotubes, which are spherical or spheroidal particles mainly composed of carbon nanotubes, and the spherical or spheroidal particles have an average diameter of 1 ⁇ m to 100 ⁇ m.
  • the porous carbon nanotube microsphere material may have any one of a microscopic spherical solid aggregate structure, a spherical aggregate structure, a spherical aggregate structure, a porous spherical aggregate structure, and a doughnut aggregate structure, but is not limited thereto;
  • the carbon nanotubes may be selected from, but not limited to, a combination of any one or more of multi-walled carbon nanotubes, double-walled carbon nanotubes, and single-walled carbon nanotubes; the carbon nanotubes may be selected from, but not limited to, untreated.
  • the pressure can be withstand a pressure range of 1 to 20 MPa, and the particle morphology is maintained after a pressure test of 20 MPa.
  • the preparation method of the above porous carbon nanotube microspheres may include: dispersing the carbon nanotubes in a solvent to form a dispersion without the aid of a surfactant, followed by spray drying, thereby preparing the porous carbon nanotube microspheres.
  • the morphology of the porous carbon nanotube microsphere material may be powder or granules.
  • the preparation method may include dispersing the carbon nanotubes in a solvent to obtain a dispersion containing no surfactant, and then inputting the dispersion into the atomization of the spray dryer. And forming minute mist droplets, and causing the mist droplets to be in parallel contact with the hot gas stream in the spray dryer to rapidly evaporate the solvent in the liquid droplets, thereby further
  • the carbon nanotubes in the liquid mist are aggregated to form porous carbon nanotube microspheres, which are then discharged from the bottom of the drying tower of the spray dryer and/or the cyclone.
  • the preparation method may include the following steps:
  • A dispersing the carbon nanotubes into a dispersant (without a surfactant) to obtain a carbon nanotube dispersion
  • step B The dispersion obtained in step A is sprayed through the nozzle of the spray dryer at a certain speed, and the inlet air temperature and the outlet air temperature are preset, and the solution is kept in a stirring state during the spraying process, and is adjusted according to different types of spray dryers. Injection speed
  • the conditions of the spray drying include: the inlet air temperature is 150-250 ° C, and the outlet air temperature is 75-150 ° C; particularly preferred spray drying conditions include: the inlet air temperature is 190-210 ° C, and the outlet air temperature is 90. ⁇ 110 °C.
  • the conditions of the spray drying may preferably include a spray rate of from 1 ml/min to 100 liters/min, which is specifically adjusted depending on the type and specifications of the spray dryer.
  • the aforementioned carbon nanometer may be selected from ordinary carbon nanotubes, carboxylated carbon nanotubes, and hydroxylated carbon nanoparticles. Rice tube, aminated carbon nanotubes, etc.
  • the dispersion contains carbon nanotubes having a concentration of 10 to 50 g/L, and more preferably, the dispersion contains a concentration of 10 to 15 g/L.
  • the solvent is an organic and/or inorganic liquid capable of uniformly dispersing carbon nanotubes.
  • a combination of any one or more of water, ammonia water, hydrochloric acid solution, ethanol, acetone, and isopropyl alcohol is preferred.
  • the solvent may be a mixture of ethanol and water in a volume ratio of 1:10.
  • a second aspect of the present application is also directed to a method for preparing a metal-skeletal carbon composite material, comprising: uniformly mixing a molten metal with a porous carbon material carrier, and cooling to obtain a metal-skeletal carbon composite material.
  • the above metal is a metal having a melting point lower than that of the porous carbon material carrier by heat or phase change temperature, such as lithium, sodium, potassium, tin or the like.
  • the preparation method of the metal lithium-skeletal carbon composite material specifically includes:
  • a skeleton carbon material is selected and prepared, and a porous carbon material having a different pore diameter is selected as a carrier for absorbing lithium metal, and a porous carbon material having a pore diameter in the range of 10 to 100 nm (preferably 10 to 50 nm) is preferable.
  • the preparation of the porous carbon material is optimal for the porous carbon nanotube microspheres prepared by the spray drying method.
  • the two were placed in a reactor filled with argon.
  • the reactor is heated and heated to above the melting point of the metal lithium.
  • stirring is carried out during the hot metal melting process.
  • the temperature was lowered to room temperature to obtain a metallic lithium-skeletal carbon composite.
  • the skeleton carbon material absorbs it into the pores of the skeleton carbon material, and similarly, a low melting point metal such as sodium, potassium or tin can be absorbed into the skeleton of the carbon material.
  • the inlet air temperature is set to 200 ° C
  • the outlet air temperature is set at 150 ° C
  • the spray pressure is set to 40 MPa
  • the injection amount is 500 mL / h.
  • 2a is a SEM picture of the carbon nanotube microsphere material
  • FIG. 2b is a comparison diagram of the porosity of the carbon nanotube microsphere and the unspherical carbon nanotube. The curve obtained from the figure shows that when the carboxylated carbon nanometer is used, The tube was converted to carboxylated carbon nanotube microspheres.
  • the pore size and pore volume distribution did not change significantly in the tested pore size range, but the average pore volume of carboxylated carbon nanotube microspheres increased due to moisture during the ball formation process. Rapid evaporation, the original dispersed carboxylated carbon nanotubes can not be re-wound into the original dense structure. Therefore, more pore volume is formed. Thereafter, the obtained carbon nanotube microspheres (hereinafter also referred to simply as "microspheres”) are subjected to particle size analysis, and the results can be referred to FIG.
  • the conductivity of the microspheres was tested. The conductivity of the microspheres was greater than 1000 S ⁇ m -1 .
  • the pressure test on the microspheres was carried out at a pressure of 1 to 20 MPa.
  • the microspheres were subjected to BET test.
  • the specific surface area of the microspheres was 294 m 2 /g.
  • the pore size distribution is from 1 to 180 nm.
  • FIG. 4a is a SEM photograph of untreated pure multi-walled carbon nanotube microspheres
  • Figure 4b is an SEM photograph of a cross-section of particles obtained by ion beam cutting of untreated pure carbon nanotube microspheres
  • Figure 4c is not A comparison of the porosity of the treated pure multi-walled carbon nanotube microspheres with the untreated pure multi-walled carbon nanotubes, which is similar to Example 1, except that the untreated multi-walled carbon nanotubes are sprayed
  • the porous carbon nanotube microspheres formed after drying have a larger pore volume.
  • the pressure test on the microspheres was carried out at a pressure of 1 to 30 MPa.
  • the microspheres were subjected to BET test.
  • the specific surface area of the microspheres was 158 m 2 /g.
  • the pore size distribution is from 1 to 160 nm.
  • the inlet air temperature is set to 200 ° C
  • the outlet air temperature is set at 150 ° C
  • the spray pressure is set to 40 MPa
  • the injection amount is 500 mL / h.
  • the conductivity of the microspheres was tested.
  • the conductivity of the microspheres was greater than 1000 S.m -1 .
  • the pressure test on the microspheres was carried out at a pressure of 1 to 20 MPa.
  • the BET test was performed on the microspheres, and the specific surface area of the microspheres was 161 m 2 /g.
  • the pore size distribution is from 1 to 165 nm.
  • the material was mixed with sulfur in a ratio of 1:4 by mass, placed in a vacuum muffle furnace and heated to 300 ° C at a heating rate of 5 ° C / min, and then incubated for 3 hours.
  • the sulfur-carbon composite material is naturally cooled to room temperature, and its morphology is shown in FIG.
  • the electrode was made using the sulfur-carbon composite as follows:
  • the sulfur-carbon composite material was weighed in a mass ratio of 70:20:10: acetylene black: LA132 (binder, Chengdu Yindile Power Technology Co., Ltd.), and ground with a 150 ⁇ m doctor blade and coated on an aluminum foil to form an electrode.
  • the lithium metal plate is used as the negative electrode, and the electrolyte is 1 mol/L LiTFSI (lithium trifluoromethanesulfonate)/DOL-DME (1,3-dioxolan-ethylene glycol dimethyl ether) (volume ratio is 1:1), the polypropylene microporous film is a separator (Celgard 2300) assembled into an analog battery.
  • the corresponding battery is charged and discharged in the range of 1.5-2.8V at a current density of 0.25A g -1 , the first discharge performance reaches 1139mAh / g, after 50 cycles, the capacity is maintained at 879mA / g, and the efficiency Also up to 85% or more.
  • the conductivity of the microspheres is 2.60*10 -2 S.cm -1 , and the pressure of the microspheres is subjected to a pressure test of 1 to 20 MPa, and the microspheres are subjected to BET.
  • the microspheres were tested to have a specific surface area of 294 m 2 /g and a pore size distribution of from 1 to 180 nm.
  • a button type supercapacitor was assembled as follows:
  • the carbon nanotube microsphere material, the conductive agent acetylene black, the binder PVDF (polyvinylidene fluoride) are mixed at a mass ratio of 8:1:1, and an appropriate amount of NMP (nitromethylpyrrolidone) is added, and the mixture is uniformly stirred, and 150 ⁇ m is used.
  • the blade was coated on an aluminum foil and dried in an oven at 80 degrees for 6 hours. Two capacitors of close mass were assembled, and the electrolyte was 1 mol/L Et 4 BNF 4 (ammonium tetraethylammonium tetrafluoroborate)/PC (propylene carbonate), and the separator was a cellulose film. The electrochemical capacitor was tested after the analog capacitor was left on.
  • Figure 9 shows the cyclic volt-ampere curve of the capacitor at a scan rate of 25 mV/s to 100 mV/s. It can be found that the symmetry of the curve is very good and basically exhibits the capacitance characteristics.
  • 10 is a charge-discharge curve of the capacitor in a voltage range of 0-2.7 V at a current density of 0.2 A/g-0.6 A/g, and the curve has a substantially symmetrical triangular distribution, indicating that the electrochemical reaction of the electrode is reversible, and the calculation is obtained.
  • the specific capacitance at current density is 16.8 F/g.
  • the lithium metal-acetylene black microspheres were obtained, and the loading amount of the metal lithium was determined to be 8.0% by weighing the weight of the acetylene black microspheres which did not absorb the lithium metal.
  • the material obtained above is used as the negative electrode of the lithium battery:
  • Fig. 11 is a view showing the charge and discharge performance of the battery cycled 25 times.
  • Preparation of carbon nanotube microspheres First, 2 g of multi-walled carbon nanotubes without any chemical treatment (Shanghai Pengxin New Material Technology Co., Ltd.) was added to 200 mL of deionized water, followed by 20 mL of absolute ethanol. Sealed and stirred, 130W ultrasonic probe was sonicated for 5 hours to evenly disperse the sample. When finished, add the sample to the spray dryer. The inlet air temperature was set to 200 ° C, the outlet air temperature was set to 150 ° C, the spray pressure was set to 40 MPa, and the injection amount was set to 500 mL / h. After drying, a porous carbon nanotube microsphere material was obtained. The microspheres were subjected to nitrogen adsorption desorption test, and the specific surface area of the microspheres was 151 m 2 /g, and the average pore diameter was 18.7 nm.
  • a lithium metal-porous carbon nanotube microsphere composite material was obtained, and the weight of the metal lithium was measured to be 15.0% by weighing the weight of the carbon nanotube microspheres which did not absorb lithium metal.
  • Fig. 12 shows a scanning electron micrograph of the prepared metallic lithium-porous carbon nanotube microsphere composite material, and it can be seen that the prepared material has a microspherical structure.
  • Preparation of carbon nanotube microspheres First, 3 g of multi-walled carbon nanotubes without any chemical treatment (Shanghai Pengxin New Material Technology Co., Ltd.) was added to 200 mL of deionized water, followed by 20 mL of absolute ethanol. Sealed and stirred, 130W ultrasonic probe was sonicated for 10 hours to evenly disperse the sample. When finished, add the sample to the spray dryer. The inlet air temperature was set to 200 ° C, the outlet air temperature was set to 120 ° C, the spray pressure was set to 40 MPa, and the injection amount was set to 500 mL / h. After drying, the carbon nanotube microsphere material was obtained. The microspheres were subjected to nitrogen adsorption desorption test, and the specific surface area of the microspheres was 197 m 2 /g, and the average pore diameter was 22.9 nm.
  • a lithium metal-porous carbon nanotube microsphere composite material was obtained, and the weight of the metal lithium was measured to be 35.0% by weighing the weight of the carbon nanotube microspheres which did not absorb lithium metal.
  • Figure 13 shows an XRD pattern of the prepared lithium metal-carbon nanotube microsphere composite. It can be seen that the prepared material contains a large amount of metallic lithium and a small amount of lithium nitride impurities.
  • porous carbon nanotube microspheres First, 4 g of multi-walled carbon nanotubes (Shanghai Pengxin New Material Technology Co., Ltd.) without any chemical treatment were added to 200 mL of deionized water, followed by 20 mL of absolute ethanol. Sealed and stirred, 130W ultrasonic probe was sonicated for 10 hours to evenly disperse the sample. When finished, add the sample to the spray dryer. The inlet air temperature was set to 200 ° C, the outlet air temperature was set to 150 ° C, the spray pressure was set to 40 MPa, and the injection amount was set to 500 mL / h. After drying, a porous carbon nanotube microsphere material was obtained. The microspheres were subjected to a nitrogen adsorption desorption test with a specific surface area of 254 m 2 /g and an average pore diameter of 31.4 nm.
  • Figure 14 shows a scanning electron micrograph of the porous carbon nanotube microspheres prepared by spray drying.
  • a lithium metal-porous carbon nanotube microsphere composite material was obtained, and the weight of the metal lithium was measured to be 43.0% by weighing the weight of the carbon nanotube microspheres which did not absorb lithium metal.
  • the effective lithium current density of the metal lithium carbon nanotube microsphere composite electrode due to its large specific surface area. It becomes small and can prolong the dendrite formation time, so no dendrites are formed after 350 hours, and the metal lithium sheet has a much smaller specific surface area, and dendrites are formed in about 60 hours, causing a short circuit of the battery.
  • the material obtained above is used as the negative electrode of the lithium battery:
  • Fig. 16 is a view showing the charge and discharge performance of the battery cycle 100 times.
  • Fig. 17 is a view showing the charge and discharge performance of the battery cycle 30 times.
  • the metal lithium-XE-2 microspheres were obtained, and the loading amount of the metal lithium was measured to be 5.0% by weighing the XE-2 of the unabsorbed lithium metal.
  • the metal sodium-carbon nanotube microspheres were obtained, and the loading amount of the metal lithium was determined to be 50.0% by weighing the weight of the carbon nanotube microspheres which did not absorb the sodium metal.

Abstract

一种多孔碳纳米管微球材料及其制备方法与应用，以及一种金属锂-骨架碳复合材料及其制备方法、二次电池负极、二次电池及一种金属-骨架碳复合材料。多孔碳纳米管微球材料是由碳纳米管组成的球形或类球状颗粒，球形或类球状颗粒的平均直径为1μm～100μm，颗粒内部由纳米管交错组成大量纳米尺度孔隙，孔径为1nm～200nm。多孔碳纳米管微球的制备方法包括：以碳纳米管与溶剂混合分散，经喷雾干燥，获得多孔碳纳米管微球。金属锂——骨架碳复合材料通过将熔融状态的金属锂与多孔碳材料载体均匀混合，冷却获得。

Description

多孔碳纳米管微球及其制备方法与应用、金属锂-骨架碳复合材料及其制备方法、负极和电池 技术领域
本申请涉及材料科学领域，特别涉及一种多孔碳纳米管微球及其制备方法与应用。本申请还涉及能源电池领域，特别是涉及一种金属锂-骨架碳复合材料及其制备方法、负极和电池。
背景技术
1991年日本NEC公司基础研究实验室的电子显微镜专家IijimaSμmio在高分辨透射电子显微镜下第一次发现碳纳米管，碳纳米管由于具有良好的导电率与机械强度，在材料增强、场致发射、药物传送、纳米电子和纳米器械等领域具有广泛的应用价值与应用前景。
不同于碳纳米管的一维线型结构，将碳纳米管制备成为多孔碳纳米管微球后，在保持了一般微球结构所拥有的优势外，由于碳纳米管自身具备良好的机械强度，多孔碳纳米管微球具备自支撑能力，球体保持了较高的机械强度，能够在承受一定外界压力的情况下保持颗粒结构的完整不受破坏。同时多孔碳纳米管微球具备大量的可控的空隙结构，提高了空间体积利用率。多孔碳纳米管微球还具备导电、化学稳定性强等特点，其性质在传统碳纳米管材料基础之上获得了巨大的改进。多孔碳纳米管微球可容纳大量的客体分子或大尺寸的客体，可以用于担载多种功能材料而形成复合功能材料，有着广阔的应用前景。以往虽然有一定碳纳米管微球结构的文献报道，但大多采用模板法与胶束法，难以获得大量的碳纳米管微球用于实际应用。而且模板法与胶束法会引入表面活性剂等物质以提高碳纳米管之间的亲和性，这造成碳纳米管主要形成球体的外壳，而在球体内部碳纳米管过少，形成的碳纳米管微球为空心结构，难以作为承载客体材料的载体材料。
另一方面，锂电池具有高能量密度，良好循环性能，环境友好等优点，在交通，通讯，电子设备等领域得到广泛应用。
目前商用的锂离子电池一般采用石墨类材料作为负极，其理论容量为372mAh/g，可逆容量一般为340mAh/g左右；而金属锂的比容量为3860mAh/g，是石墨负极的10倍以上，能够采用金属锂作为锂离子电池负极，将能够大幅提高锂离子电池的能量密度。但是采用金属锂作为负极材料制备的电池，在充电过程中，锂离子在金属锂负极上会发生不均匀的沉积，形成枝晶刺穿隔膜造成短路并可能导致电池发生燃烧、爆炸等危险，因此金属锂负极一直没有得到商业化应用。美国FMC公司(专利US 8,021,496 B2，US 2013/0181160 A1，CN102255080 A)使用熔融乳化的方法制备出20μm～100μm的金属锂颗粒，之后再其表面进行修饰处理，将此材料制备成电极片作为电池负极使用，能够提高金属锂的比表面积，降低负极在充放电过程中的有效面电流密度，缓解枝晶的生长。韩国Woo Young Yoon课题组，(参考文献Advanced Functional Materials2013，23，1019-1027，Journal of Power Sources 2010，195，6143-6147.)采用熔融乳化的方法制备出金属锂颗粒，在金属锂颗粒表面进行修饰，之后压片制备电极，也能够提高金属锂用于负极时电池的安全性。中国天津中能锂业有限公司(专利CN 102122709A)将制备好的金属锂颗粒压制到石墨负极中，得到含有金属锂的负极，这可以弥补锂离子电池循环过程中正极材料中有限的锂在循环过程中发生的损耗。但是，以上采用熔融乳化的方法制备金属锂颗粒，需要将金属锂在高温剧烈搅拌的条件下在的高沸点惰性溶液中进行分散，分散结束之后，需要多次的洗涤才能获得金属锂微粒，步骤繁琐，制备过程对于设备要求比较苛刻。
发明内容
鉴于现有技术的不足，在本发明的第一方面中，本发明的一个目的在于提供一种新型的多孔碳纳米管微球材料。
本发明的另一个目的在于提供一种多孔碳纳米管微球材料的制备方法，其具有操作简单、成本低、生产效率高等特点、可实现多孔碳纳米管微球材料的规模化生产。
本发明的又一个目的在于提供前述多孔碳纳米管微球材料在制备电池或超级电容器中的应用，所述电池包括锂硫电池或燃料电池。
为实现前述发明目的，本发明采用的技术方案如下：
一种多孔碳纳米管微球材料，其是由碳纳米管组成的球形或类球状颗粒，颗粒内部由碳纳米管交错组成大量纳米尺度孔隙，所述球形或类球状颗粒的平均直径为1μm～100μm。
进一步的，所述多孔碳纳米管微球材料至少具有微小球状实体聚集结构、球形聚集结构、类球形聚集结构、多孔球形聚集结构和面包圈形聚集结构中的任意一种。
前述任一种碳纳米管微球材料的制备方法，包括：将碳纳米管分散于溶剂中形成分散液后喷雾干燥，从而制得所述多孔碳纳米管微球材料。
其中，分散可以在没有表面活性剂的辅助下进行。
喷雾干燥的条件包括：进风温度为150～250℃，出风温度为75℃以上，例如75～150℃，但优选出风温度为90℃以上。
进一步的，该制备方法的具体步骤可包括：将碳纳米管分散在溶剂中获得分散液，而后将分散液输入喷雾干燥机的雾化器中，通过控制进液速度、雾化条件、热风温度与速度，使含有碳纳米管的液滴中的溶剂迅速蒸发，进而使所述液状雾滴中的碳纳米管聚集形成多孔碳纳米管微球，其后将所述多孔碳纳米管微球从所述喷雾干燥机的干燥塔底部和/或旋风分离器排出。
与现有技术相比，本发明的优点包括：该多孔碳纳米管微球材料内部完全由碳纳米管相互之间交错堆积形成，在颗粒内外都具有大量的纳米尺度的空隙，具有较大的孔隙尺寸与良好的机械强度，可作为纳米科学的载体材料等广泛应用于各个领域，且其制备方法简单，可控性强，成本低廉，易实现规模化生产。尤其是，本发明的制备方法不需要表面活性剂的辅助，完全靠碳纳米管相互之间交错堆积而形成颗粒，因此，颗粒所含孔隙尺寸较大且机械强度高，适合用作担载客体材料的载体材料。
在本发明的第二方面中，基于第一方面的多孔碳纳米管微球材料，提供一 种金属锂-骨架碳复合材料及其制备方法、负极和电池，以克服现有技术中的不足。
为实现上述目的，本发明提供如下技术方案：
本申请实施例公开了一种金属-骨架碳复合材料，包括多孔碳材料载体以及形成于所述碳材料载体孔隙中的金属。
优选的，所述金属包括锂、钠和钾。
优选的，在上述的金属-骨架碳复合材料中，所述碳材料包括碳纤维微球、多孔碳纳米管微球和乙炔黑。
优选的，在上述的金属-骨架碳复合材料中，所述多孔碳纳米管微球是本发明第一方面中的多孔碳纳米管微球材料。
优选的，在上述的金属-骨架碳复合材料中，所述多孔碳纳米管微球的平均孔径为10nm～50nm。
优选的，金属-骨架碳复合材料中金属锂的负载量为5质量％至80质量％，更优选30-50质量％。
本申请实施例还公开了一种采用上述金属锂-骨架碳复合材料的电池负极。
优选的，本发明的电池负极为二次电池负极。
相应地，本申请实施例还公开了一种电池，其包括上述的负极。
优选的，本发明的电池为二次电池。
优选的，上述的二次电池为锂-硫电池、金属锂-氧化物电池、金属锂-聚合物电池或可充电锂离子电池。
本申请实施例还公开了一种金属锂-骨架碳复合材料的制备方法，将熔融状态的金属锂与多孔的碳材料载体均匀混合，冷却获得金属锂-骨架碳复合材料。
优选的，在上述的金属锂-骨架碳复合材料的制备方法中，所述碳材料载体为多孔碳纳米管微球，该多孔碳纳米管微球通过上述第一方面中的多孔碳纳米管微球材料的制备方法制备。
与现有技术相比，本发明的优点在于：本发明制备出的金属锂-骨架碳复合材料可以应用于各式各样的锂电池，可应用于金属锂-氧化物电池，金属锂-聚合物电池，可充电锂离子电池。值得注意的一个领域是可充电锂离子电池在可携带的电子设备，和混合动力汽车的应用，在这些应用中，希望二次锂电池在保证安全性前提下，提供最高比容量和良好循环性能，而金属锂作为最理想的负 极材料，由于在充放电过程中产生枝晶，安全性低差，所以不能直接使用，本发明制备出金属锂-骨架碳复合材料可以抑制枝晶形成，提高电池的安全性，并且提供较高的比容量和良好的循环性能。
附图说明
为了更清楚地说明本申请或现有技术中的技术方案，下面将对本申请或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请中记载的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明一典型实施方案中一种多孔碳纳米管微球材料制备系统的结构示意图，其中：1-空气过滤器、2-加热器、3-热风分配器、4-干燥室、5-过滤器、6-泵、7-离心喷头、8-旋风分离器、9-风机、10-料液槽。
图2a-图2b分别是实施例1所获羧基化碳纳米管微球的SEM图及羧基化碳纳米管微球与未成球碳纳米管孔隙率的对比图。从图2b中所获得曲线可知当羧基化碳纳米管转换为羧基化碳纳米管微球，羧基化碳纳米管微球的平均孔容积较纯的羧基化碳纳米管增大。
图3是实施例1使用浓度为10g/L的羧基碳管分散液制备的羧基化碳纳米管微球的粒径分布统计图。
图4a、4b、4c分别是实施例2所获未经处理的多孔多壁碳纳米管微球的SEM图、未经处理的多孔多壁碳纳米管微球的截面图和未经处理的多孔多壁碳纳米管微球与未成球碳纳米管孔隙率的对比图。
图5是实施例2所获未经任何化学处理的多孔多壁碳纳米管微球的粒径分布统计图。
图6是实施例3所获羟基化多壁碳纳米管微球的SEM图。
图7是实施例4制备的碳硫复合材料的SEM图。
图8a、8b分别是实施例4制备的碳硫复合材料首轮充放电曲线和电池循环性能图。
图9是实施例5制备的碳纳米管微球超级电容器循环伏安曲线图。
图10是实施例5制备的碳纳米管微球超级电容器充放电曲线。
图11所示为本发明实施例7中所获得金属锂-乙炔黑复合材料与磷酸铁锂构 成的电池充放电循环性能图；
图12所示为本发明实施例8中制备出的金属锂-多孔碳纳米管微球复合材料扫描电镜图，图12a(左)的放大倍数为500倍，图12b(右)为10000倍；
图13所示为本发明实施例9中所获得金属锂-多孔碳纳米管微球复合材料(上部)和多孔碳纳米管微球(下部)的X射线粉末衍射图，其中含有明显的金属锂的衍射峰与少量氮化锂杂质峰；
图14所示为本发明实施例10中所获得多孔碳纳米管微球的扫描电镜照片，左图的放大倍数为500倍，右图为10000倍；
图15所示为本发明实施例10中所获得金属锂-多孔碳纳米管微球复合材料与金属锂片构成的电池由枝晶造成短路的时间图，该电池在0.2mA恒流充电(电流密度0.1mA/cm2)测试枝晶造成短路的时间，对比实验为金属锂片与金属锂片构成的电池；
图16所示为本发明实施例10中所获得金属锂-多孔碳纳米管微球复合材料作为负极，尖晶石锰酸锂作为正极的锰酸锂组成的模拟电池充放电循环性能图；
图17所示为本发明实施例10中所获得金属锂-多孔碳纳米管微球复合材料与磷酸铁锂构成的电池充放电循环性能图。
具体实施方式
如前所述，鉴于现有技术中的不足，本案发明人经大量研究和实践，提出了本发明的技术方案，以下具体解释说明。
第一方面的实施方案
本发明的一个方面提供了一种多孔碳纳米管微球材料，它是由碳纳米管组成的球形或类球状颗粒，颗粒内部由碳纳米管交错组成大量纳米尺度孔隙，所述球形或类球状颗粒的平均直径为1μm～100μm，优选为1μm～25μm。
进一步的，所述多孔碳纳米管微球材料可具有微小球状实体聚集结构、球形聚集结构、类球形聚集结构、多孔球形聚集结构和面包圈形聚集结构中的任意一种，但不限于此。
进一步的，所述碳纳米管可选自但不限于多壁碳纳米管、双壁碳纳米管和 单壁碳纳米管中的任意一种或多种的组合，优选多壁碳纳米管。
进一步的，所述碳纳米管可选自但不限于商品化碳纳米管、纯化碳纳米管(无催化剂的纯化碳纳米管)和经过表面功能化处理的碳纳米管中的任意一种或多种的组合。
对于前述经过表面功能化处理的碳纳米管，其中修饰于碳纳米管表面的基团可选自但不限于-COOH、-OH、-NH2等基团。
优选的，所述碳纳米管采用不含催化剂的纯净碳纳米管，特别是不含催化剂的纯净多壁碳纳米管。
进一步的，通过对所述多孔碳纳米管微球接受压力测试最大可承受压力可达20MPa。此处，可承受压力指的是在压力释放后仍然能够保持颗粒的多孔结构。在本发明中，经20MPa压力测试后，依然保持球体不破裂。
进一步的，通过对所述多孔碳纳米管微球进行比表面积测试，可以发现其比表面积为100～1500m2/g，优选为150～500m2/g。
进一步的，所述多孔碳纳米管微球内所含孔隙的孔径分布为1～200nm，优选为1～50nm。
进一步的，经测试表面，前述碳纳米管微球电导率为0.1～100S.cm-1，优选为10～100S.cm-1。
本发明还提供了一种多孔碳纳米管微球的制备方法，包括：在不需要表面活性剂的辅助下，将碳纳米管分散于溶剂中形成分散液后喷雾干燥，从而制得所述多孔碳纳米管微球。
本发明所述的碳纳米管微球材料的形态可以为粉末状或颗粒。
更为具体的，作为本发明的可行实施方案之一，请参阅图1，该制备方法可以包括：将碳纳米管分散于溶剂中获得在料液槽10中的不含表面活性剂分散液，而后将分散液经由过滤器5与泵6输入喷雾干燥机的离心喷头7中，并形成微小的雾状液滴，且使所述雾状液滴在所述喷雾干燥机中与由空气过滤器1及加热器2及热风分配器3热气流产生的热气流并流接触(此处瞬时热气流温度为物料进风温度)，进入干燥塔4(此时物料干燥温度为物料出风温度)，使所述液状雾滴中的溶剂迅速蒸发，进而使所述液状雾滴中的碳纳米管聚集形成碳纳米管微球，其后将所述碳纳米管微球从所述喷雾干燥机的干燥塔4底部和/或旋风分离器8收集，热空气由风机9抽走。
在一典型实施案例中，该制备方法可以包括如下步骤：
A、将碳纳米管通过超声处理分散到分散溶剂(不含表面活性剂)中，获得碳纳米管分散液；
B、将步骤A中获得分散液以一定速度通过喷雾干燥机的喷嘴喷出，预设定进风温度和出风温度，喷雾过程中保持溶液为搅拌状态，视不同型号的喷雾干燥机而调整注液速度；
C、自然冷却，即获得所需多孔碳纳米管微球。
优选的，前述喷雾干燥的条件包括：进风温度为150～250℃，出风温度可根据实际情况调节，例如为75℃以上，如75～150℃，或者为90℃以上；尤为优选的喷雾干燥条件包括：进风温度为190～210℃，出风温度为90～110℃。
进一步的，喷雾干燥的条件还可优选包括：喷雾速度为1毫升/小时～10000升/小时，优选1毫升/分钟至100升/分钟，其根据喷雾干燥机型号及规格的不同而具体调整。
优选的，前述碳纳米可选自普通碳纳米管，羧基化碳纳米管，羟基化碳纳米管，氨基化碳纳米管等。
优选的，所述分散液包含浓度为10～50g/L的碳纳米管，进一步优选的，分散液包含浓度为10～15g/L。
进一步的，前述溶剂采用能够使碳纳米管均匀分散的有机和/或无机液体，例如，优选水、氨水、盐酸溶液、乙醇、丙酮、异丙醇的任意一种或多种的组合。
而在一更为具体的优选实施案例中，所述溶剂可以是体积比为1∶10的乙醇与水的混合物。
又及，在本发明中所述的喷雾干燥机是可以将液料喷成雾状，并使其与高温热源环境迅速接触而得以获得固定形貌以及被干燥成成品的一类设备的总称，其并不局限于图1所示的结构，亦可为业界所知的其它具有相近功能之设备。
在本发明中，本案发明人创造性地将喷雾干燥这一传统技术用于多孔碳纳米管微球的制备，在液滴蒸干过程中，分散在其中的碳纳米管受到液滴收缩的作用发生团聚，但是在团聚到一定程度后，由于碳纳米管自身具有良好的机械强度而阻止了进一步的压缩，从而获得具备一定尺寸、孔隙率的由碳纳米管相互交错堆叠形成的多孔微球结构，微球内部充满纳米尺寸的空隙。本发明仅使 用碳纳米管与常规分散溶剂进行喷雾干燥即可获得碳纳米管微球，极大地简化了碳纳米管微球的制备工艺，并降低了生产成本，并且所获多孔碳纳米管微球粒径规整，尺寸可控，具有良好的机械强度、导电性质、孔隙率，可作为碳纳米管的一种拓展材料在电极材料，医药输送等领域获得广泛应用。
例如，前述多孔碳纳米管微球可以应用于制备电池、超级电容器等，例如，锂硫电池电极、超级电容器电极、燃料电池电极。
作为其中的实施案例之一，可以前述多孔碳纳米管微球制备电极材料。例如，通过采用业界所知的方式将所述多孔碳纳米管微球与硫等混合形成硫碳复合材料，再与炭黑、乙炔黑和其它辅助材料，例如赋形剂、粘结剂等组合制浆，再涂覆到铝箔等集流体上，从而形成可应用于锂硫电池的正极材料，继而通过将该正极材料与负极材料、电解质等组合，可形成一次、二次锂电池等。
作为其中的实施案例之一，可以前述多孔碳纳米管微球与炭黑、乙炔黑和其它辅助材料，例如赋形剂、粘结剂等组合制浆，再涂覆到铝箔等基材上形成电极片，继而通过将该电极片与另一电极片、隔膜、电解质等组合，可形成超级电容器。下面以具体实施例对本发明的技术方案作进一步说明，但本发明的保护范围不限于此。
第二方面的实施方案
本申请的第二方面涉及一种金属锂-骨架碳复合材料，包括多孔的碳材料载体以及形成于所述碳材料载体孔隙中的金属锂。
上述的碳材料骨架结构可以是以碳纤维、碳纳米管等材料组成的微球(平均孔径10-50nm)结构，还可以使用乙炔黑。还可以选用平均孔径在10-100nm范围内的其他碳骨架材料作为吸收熔融金属锂的载体。
金属锂在金属锂-骨架碳复合材料中的质量占比一般为5％至80％，更优选30％至50％。
作为优选的，碳材料骨架使用碳纳米管通过喷雾干燥制备得到的微球，它是主要由碳纳米管组成的球形或类球状颗粒，所述球形或类球状颗粒的平均直径为1μm～100μm，优选为1μm～25μm；多孔碳纳米管微球材料可具有微小球状实体聚集结构、球形聚集结构、类球形聚集结构、多孔球形聚集结构和面包圈形聚集结构中的任意一种，但不限于此；碳纳米管可选自但不限于多壁碳纳 米管、双壁碳纳米管和单壁碳纳米管中的任意一种或多种的组合；碳纳米管可选自但不限于未经处理的纯净商品化碳纳米管、无催化剂的纯化碳纳米管和经过表面功能化处理的碳纳米管中的任意一种或多种的组合，对于前述经过表面功能化处理的碳纳米管，其中修饰于碳纳米管表面的基团可选自但不限于-COOH、-OH、-NH2等基团；所述碳纳米管优选采用不含催化剂的纯净碳纳米管，特别是不含催化剂的纯净多壁碳纳米管。
进一步的，通过对所述多孔碳纳米管微球接受压力测试，可以发现其可承受压力范围为1～20MPa，且经20MPa压力测试后，依然保持颗粒形貌。
上述多孔碳纳米管微球的制备方法可以包括：在没有表面活性剂的辅助下，将碳纳米管分散于溶剂中形成分散液后喷雾干燥，从而制得所述多孔碳纳米管微球。
所述的多孔碳纳米管微球材料的形态可以为粉末状或颗粒。
更为具体的，作为本发明的可行实施方案之一，该制备方法可以包括：将碳纳米管分散在溶剂中获得不含表面活性剂的分散液，而后将分散液输入喷雾干燥机的雾化器中，并形成微小的雾状液滴，且使所述雾状液滴在所述喷雾干燥机中与热气流并流接触，使所述液状雾滴中的溶剂迅速蒸发，进而使所述液状雾滴中的碳纳米管聚集形成多孔碳纳米管微球，其后将所述多孔碳纳米管微球从所述喷雾干燥机的干燥塔底部和/或旋风分离器排出。
在一典型实施例中，该制备方法可以包括如下步骤：
A、将碳纳米管分散到分散剂(不含表面活性剂)中，获得碳纳米管分散液；
B、将步骤A中获得分散液以一定速度通过喷雾干燥机的喷嘴喷出，预设定入风温度和出风温度，喷雾过程中保持溶液为搅拌状态，视不同型号的喷雾干燥机而调整注液速度；
C、自然冷却，即获得所需多孔碳纳米管微球。
优选的，前述喷雾干燥的条件包括：进风温度为150～250℃，出风温度为75～150℃；尤为优选的喷雾干燥条件包括：进风温度为190～210℃，出风温度为90～110℃。
进一步的，喷雾干燥的条件还可优选包括：喷雾速度为1毫升/分钟至100升/分钟，其根据喷雾干燥机型号及规格的不同而具体调整。
优选的，前述碳纳米可选自普通碳纳米管，羧基化碳纳米管，羟基化碳纳 米管，氨基化碳纳米管等。
优选的，所述分散液包含浓度为10～50g/L的碳纳米管，进一步优选的，分散液包含浓度为10～15g/L。
进一步的，前述溶剂采用能够使碳纳米管均匀分散的有机和/或无机液体，例如，优选水、氨水、盐酸溶液、乙醇、丙酮、异丙醇的任意一种或多种的组合。
而在一更为具体的优选实施案例中，所述溶剂可以是体积比为1∶10的乙醇与水的混合物。
本申请的第二方面还涉及一种金属-骨架碳复合材料的制备方法，包括：将熔融状态的金属与多孔碳材料载体混合均匀，冷却获得金属-骨架碳复合材料。
上述的金属为熔点低于多孔碳材料载体受热破坏或相变温度的金属，例如锂、钠、钾、锡等。
例如，金属锂-骨架碳复合材料的制备方法具体包括：
第一步，选取、制备骨架碳材料，选取不同孔径的多孔碳材料作为吸收金属锂的载体，其中优选孔径在10-100nm(优选10-50nm)范围内的多孔碳材料。
其中多孔碳材料的制备以喷雾干燥法制备出的多孔碳纳米管微球为最优。
第二步，称取一定比例的金属锂(电池级)与骨架碳材料。
第三步，将二者放置于充满氩气的反应器中。
第四步，加热反应器，加热到金属锂熔点以上。
第五步，在金属锂热熔过程中进行搅拌。
第六步，混合结束后降低至室温，获得金属锂-骨架碳复合材料。
通过加热将金属锂熔融之后，骨架碳材料将其吸收至骨架碳材料的孔隙中，同样也可根据此将钠、钾、锡等低熔点金属吸收到碳材料骨架中。
为使本发明的目的、技术方案和优点更加清楚，下面结合附图对本发明的具体实施例进行详细说明。附图中所示和根据附图描述的本发明的实施方式仅仅是示例性的，并且本发明并不限于这些实施方式。
在此，还需要说明的是，为了避免因不必要的细节而模糊了本发明，在附图中仅仅示出了与根据本发明的方案密切相关的结构和/或处理步骤，而省略了与本发明关系不大的其他细节。
实施例1
首先将4g羧基含量为3.86wt％多壁碳纳米管(南京吉仓纳米科技有限公司，型号JCMT-95-8-20-COOH)加入200ml去离子水，后加入20mL 37％浓氨水。密封搅拌，130W超声探头超声处理10小时，使样品均匀分散。完毕后将样品加入喷雾干燥机(上海雅程仪器设备有限公司，型号YC-015)。进风温度设定为200℃，出风温度设定在150℃，喷雾压力设定为40MPa，进样量为500mL/h，干燥后即得到羧基化碳纳米管微球材料，而后对所得样品进行比表面积与孔径分布测试。参阅图2a为所述碳纳米管微球材料的SEM图片，图2b为所述碳纳米管微球与未成球碳纳米管孔隙率的对比图，从图中所获得曲线可知当羧基化碳纳米管转换为羧基化碳纳米管微球，在所测试孔径区间内孔径与孔容积分布未有明显变化，但羧基化碳纳米管微球的平均孔容积增大，这是由于成球过程中水分迅速蒸发，原本分散的羧基化碳纳米管来不及重新缠绕成原先致密结构。故形成了更多的孔容积。之后，对所获碳纳米管微球(下文亦简称为“微球”)进行粒径分析，其结果可参阅图3。对微球进行电导率测试，微球电导率大于1000S·m-1，对微球进行压力测试微球承受压力为1～20MPa，对微球进行BET测试，微球比表面积为294m2/g，孔径分布为1～180nm。
实施例2
首先将4g未经任何化学处理的多壁碳纳米管(南京吉仓纳米科技有限公司，型号JCMT-95-30-17)加入200ml去离子水，后加入20mL无水乙醇。密封搅拌，130W超声探头超声处理10小时，使样品均匀分散。完毕后将样品加入喷雾干燥机(上海雅程仪器设备有限公司，型号YC-015)。进风温度设定为200℃，出风温度设定在150℃，喷雾压力设定为40MPa，进样量设定为500mL/h，干燥后即得到碳纳米管微球材料，后对所得样品进行比表面积与孔径分布测试。图4a为未经处理的纯净多壁碳纳米管微球的SEM照片，图4b为未经处理的纯的碳纳米管微球使用离子束切割获得的颗粒截面的SEM照片，图4c是未经处理的纯净多壁碳纳米管微球与未成球未经处理的纯净多壁碳纳米管孔隙率的对 比图，其与实施例1类似，不同点在于未经处理的多壁碳纳米管在喷雾干燥后形成的多孔碳纳米管微球具有更大的孔容积。其原因可能是普通碳纳米管相比于羧基化碳纳米管分散性稍差，故分散于水中时无法形成更为理想的分散状态，因此喷雾干燥得到的微球，微球内部由碳纳米管相互交织形成的孔隙更多。之后，对所获微球进行粒径分析，其结果请参阅图5。对微球进行电导率测试，微球电导率为1600S.m-1，对微球进行压力测试微球承受压力为1～30MPa，对微球进行BET测试，微球比表面积为158m2/g，孔径分布为1～160nm。
实施例3
首先将4g羟基含量为3.86％多壁碳纳米管(南京吉仓纳米科技有限公司，型号JCMT-95-8-20-COOH)加入200ml去离子水，后加入20mL 37％浓氨水。密封搅拌，130W超声探头超声处理10小时，使样品均匀分散。完毕后将样品加入喷雾干燥机(上海雅程仪器设备有限公司，型号YC-015)。进风温度设定为200℃，出风温度设定在150℃，喷雾压力设定为40MPa，进样量为500mL/h，干燥后即得到羟基碳纳米管微球材料，其形态和粒径可参阅图6。对微球进行电导率测试，微球电导率大于1000S.m-1，对微球进行压力测试微球承受压力为1～20MPa，对微球进行BET测试，微球比表面积为161m2/g，孔径分布为1～165nm。
实施例4
首先将4g普通多壁碳纳米管，至于200mL去离子水，后加入20mL无水乙醇。密封搅拌，130W超声探头超声处理10小时，使样品均匀分散。完毕后将样品加入喷雾干燥机。进风温度设定为200℃，出风温度设定在150℃，喷雾压力设定为40MPa，进样量为500mL/h，干燥后即得到多孔碳纳米管微球，其形态和粒径可参阅图4a，而其孔隙率与实施例2基本相近。后将该材料与硫按1∶4质量比例混合，置于真空马弗炉以5℃/min升温速度加热至300℃，后保温3小时。自然冷却至室温，即得所述硫碳复合材料，其形态见图7。
用该硫碳复合材料按下述方法制成电极：
以70∶20∶10的质量比分别称取硫碳复合材料∶乙炔黑∶LA132(粘结剂，成都茵地乐电源科技有限公司)，研磨以150μm刮刀均匀后涂覆在铝箔上制成电 极，采用金属锂片为负极，电解液为1mol/L LiTFSI(三氟甲烷磺酸亚胺锂)/DOL-DME(1，3-二氧戊环-乙二醇二甲醚)(体积比为1∶1)，聚丙烯微孔薄膜为隔膜(Celgard 2300)，组装成模拟电池。参阅图8a-8b，相应电池在0.25A g-1的电流密度下1.5-2.8V电压范围内充放电，首次放电性能达到1139mAh/g，50次循环后，容量保持在879mA/g，且效率同样高达85％以上。
实施例5
首先将4g未经任何化学处理的多壁碳纳米管加入200ml去离子水，后加入20mL无水乙醇。密封搅拌，130W超声探头超声处理10小时，使样品均匀分散。完毕后将样品加入喷雾干燥机。进风温度设定为200℃，出风温度设定在150℃，喷雾压力设定为40MPa，进样量设定为500mL/h，干燥后即得到多孔碳纳米管微球材料，其形态与实施例2基本相近，对微球进行电导率测试，微球电导率为2.60*10-2S.cm-1，对微球进行压力测试微球承受压力为1～20MPa，对微球进行BET测试，微球比表面积为294m2/g，孔径分布为1～180nm。
用本实施例所得的碳纳米管微球材料按下述方法组装扣式超级电容器：
将碳纳米管微球材料、导电剂乙炔黑、粘结剂PVDF(聚偏氟乙烯)按照质量百分数比为8∶1∶1混合，加入适量NMP(氮甲基吡咯烷酮)，搅拌均匀，用150μm刮刀涂覆在铝箔上，置于烘箱80度下干燥6小时。取两片质量接近的电极片组装电容器，使用电解液为1mol/L Et4BNF4(四乙基四氟硼酸铵)/PC(碳酸丙烯酯)，隔膜为一种纤维素膜。模拟电容器搁置活化后进行电化学性能测试。图9为该电容器在25mV/s-100mV/s扫描速率下的循环伏安曲线，可以发现曲线的对称性很好，基本表现出电容特性。图10为该电容器在0.2A/g-0.6A/g电流密度下0-2.7V电压范围内的充放电曲线，曲线呈大致对称的三角形分布，说明电极电化学反应可逆性好，计算得到该电流密度下的比电容为16.8F/g。
实施例6
首先秤取200mg电池级金属锂(重庆昆瑜锂业有限公司)与200mg商用多孔碳(平均孔径2.6nm)(多孔碳JCAC-2000)共同置于对金属锂惰性的加热反应器中，在氩气保护下，加热至金属锂熔化的温度，剧烈搅拌，持续数分钟，混合过程中发现多孔碳不能作为载体吸收熔融的金属锂，所形成的复合物成块 状，说明平均孔径过小，不能有效的吸收熔融金属锂。
实施例7
首先秤取200mg电池级金属锂(重庆昆瑜锂业有限公司)与200mg商用的乙炔黑(平均孔径14.4nm)(Alfa Aeser试剂公司)共同置于对金属锂惰性的加热反应器中，加热至金属锂熔化的温度，剧烈搅拌，持续6-8分钟，混合结束之后，降温至室温，整个过程在氩气气氛中进行。
得到金属锂-乙炔黑微球，通过称重对比未吸收金属锂的乙炔黑微球的重量，测得其中金属锂的负载量为：8.0％。
用上述得到的材料作为锂电池的负极：
锂离子电池正极材料为LiFePO4∶PVFD∶AB＝88∶5∶7(PVDF：聚偏氟乙烯；AB：导电炭黑)，厚度为150um，电解液为1mol/L LiPF6/EC-DMC(1∶1vol)(EC：碳酸乙烯酯；DMC：碳酸二甲酯)，组装成扣式电池(CR 2025)，循环25次，整个循环过程中电池的库伦效率不高，随着循环的进行，库伦效率趋于稳定。图11为该电池的循环25次的充放电性能示意图。
实施例8
碳纳米管微球的制备：首先将2g未经任何化学处理的多壁碳纳米管(上海鹏芯新材料科技有限公司)加入200mL去离子水，后加入20mL无水乙醇。密封搅拌，130W超声探头超声处理5小时，使样品均匀分散。完毕后将样品加入喷雾干燥机。进风温度设定为200℃，出风温度设定在150℃，喷雾压力设定为40MPa，进样量设定为500mL/h，干燥后即得到多孔碳纳米管微球材料。对微球进行氮气吸附脱附测试，微球比表面积为151m2/g，平均孔径为18.7nm。
首先称取100mg电池级金属锂和100mg多孔碳纳米管微球(碳纳米管通过喷雾干燥获得，平均孔径为18.7nm)置于对金属锂惰性的加热器中，加热至220℃(高于金属锂的熔点)，搅拌，持续6分钟，混合结束，降温至室温，整个过程在氩气气氛中进行。
得到金属锂-多孔碳纳米管微球复合材料，通过称重对比未吸收金属锂的碳纳米管微球的重量，测得其中金属锂的负载量为：15.0％。
图12显示了制备出的金属锂-多孔碳纳米管微球复合材料扫描电镜图，可以看出制备出的材料为微米球形结构。
实施例9
碳纳米管微球的制备：首先将3g未经任何化学处理的多壁碳纳米管(上海鹏芯新材料科技有限公司)加入200mL去离子水，后加入20mL无水乙醇。密封搅拌，130W超声探头超声处理10小时，使样品均匀分散。完毕后将样品加入喷雾干燥机。进风温度设定为200℃，出风温度设定在120℃，喷雾压力设定为40MPa，进样量设定为500mL/h，干燥后即得到碳纳米管微球材料。对微球进行氮气吸附脱附测试，微球比表面积为197m2/g，平均孔径为22.9nm。
首先称取100mg电池级金属锂和100mg碳纳米管微球(碳纳米管通过喷雾干燥获得，平均孔径为22.9nm)置于对金属锂惰性的加热器中，加热至220℃(高于金属锂的熔点)，搅拌，持续6分钟，混合结束，降温至室温，整个过程在氩气气氛中进行。
得到金属锂-多孔碳纳米管微球复合材料，通过称重对比未吸收金属锂的碳纳米管微球的重量，测得其中金属锂的负载量为：35.0％。
图13显示制备的金属锂-碳纳米管微球复合材料的XRD图，可以看出制备的材料中含有大量金属锂单质，同时含有少量氮化锂杂质的峰。
实施例10
多孔碳纳米管微球的制备：首先将4g未经任何化学处理的多壁碳纳米管(上海鹏芯新材料科技有限公司)加入200mL去离子水，后加入20mL无水乙醇。密封搅拌，130W超声探头超声处理10小时，使样品均匀分散。完毕后将样品加入喷雾干燥机。进风温度设定为200℃，出风温度设定在150℃，喷雾压力设定为40MPa，进样量设定为500mL/h，干燥后即得到多孔碳纳米管微球材料。对微球进行氮气吸附脱附测试，微球比表面积为254m2/g，平均孔径为31.4nm。
图14显示了喷雾干燥制备得到的多孔碳纳米管微球的扫描电镜照片。
首先称取200mg电池级金属锂和200mg碳纳米管微球(碳纳米管通过喷雾干燥获得，平均孔径为31.4nm)置于对金属锂惰性的加热器中，加热至220℃(高于金属锂的熔点)，搅拌，持续6分钟，混合结束，降温至室温，整个过程在氩气气氛中进行。
得到金属锂-多孔碳纳米管微球复合材料，通过称重对比未吸收金属锂的碳纳米管微球的重量，测得其中金属锂的负载量为：43.0％。
图15显示金属锂和金属锂-多孔碳纳米管微球复合材料电极作为工作电极 分别和金属锂片构成的半电池，之后将金属锂片中的锂电镀至工作电极，研究枝晶的形成时间，从图中可以看出在同样的电流密0.1mA/cm2度条件下，根据Sand’time公式可知，金属锂碳纳米管微球复合材料电极由于自身的大的比表面积，有效电极电流密度变得很小，可以延长枝晶形成时间，所以在350小时之后都无枝晶生成，而金属锂片的比表面积要小的多，在60小时左右形成枝晶，造成电池的短路。
用上述得到的材料作为锂电池的负极：
锂离子电池正极材料为LiMnO4∶PVFD∶AB＝88∶5∶7，厚度为150μm，电解液为1mol/L LiPF6/EC-DMC(1∶1vol)，组装成扣式电池(CR 2025)，采用1C电流充放电，循环100次，电池容量几乎没有损失。图16为该电池循环100次的充放电性能示意图。
锂离子电池正极材料为LiFePO4∶PVFD∶AB＝88∶5∶7，厚度为150μm，电解液为1mol/L LiPF6/EC-DMC(1∶1vol)，组装成扣式电池(CR 2025)，循环30次，电池的比容量几乎没有损失。图17为该电池的循环30次的充放电性能示意图。
实施例11
首先秤取200mg电池级金属锂与200mg商品XE-2碳材料(平均孔径10nm)(青岛纽森克新材料有限公司)共同置于对金属锂惰性的加热器中，加热至金属锂熔化的温度，剧烈搅拌，持续6-8分钟，混合结束之后，降温至室温，整个过程在氩气气氛中进行。
得到金属锂-XE-2微球，通过称重对比未吸收金属锂的XE-2的重量，测得其中金属锂的负载量为：5.0％。
实施例12
首先秤取200mg金属钠(国药集团化学试剂有限公司)与200mg碳纳米管微球(由碳纳米管通过喷雾干燥获得，平均孔径为31.4nm)置于对金属锂惰性的加热器中，加热至110℃(高于金属钠的熔点)，搅拌，持续10分钟，混合结束，降温至室温，整个过程在氩气气氛中进行。
得到金属钠-碳纳米管微球，通过称重对比未吸收金属钠的碳纳米管微球的重量，测得其中金属锂的负载量为：50.0％。
应当理解，以上说明及附图所示的实施例，不可解释为限定本发明的设计 思想。在本发明的技术领域里持有相同知识者可以将本发明的技术性思想以多样的形态改良变更，这样的改良及变更应理解为属于本发明的保护范围内。
还需要说明的是，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。
本申请要求2014年3月21日提交的中国专利申请201410106376.0和2014年8月13日提交的中国专利申请201410395114.0的优先权，这两件中国专利申请通过引用以其全文形式结合在本文中。

Claims (26)

  1. 一种多孔碳纳米管微球材料，其是由碳纳米管组成的球形或类球状颗粒，颗粒内部由碳纳米管交错组成大量纳米尺度孔隙，所述球形或类球状颗粒的平均直径为1μm～100μm。
  2. 根据权利要求1所述的多孔碳纳米管微球材料，其至少具有微小球状实体聚集结构、球形聚集结构、类球形聚集结构、多孔球形聚集结构和面包圈形聚集结构中的任意一种。
  3. 根据权利要求1-2中任一项所述的多孔碳纳米管微球材料，其中所述球形或类球状颗粒的平均直径为1μm～25μm。
  4. 根据权利要求1-3中任一项所述的多孔碳纳米管微球材料，其中所述碳纳米管微球材料的最大可承受压力为20MPa。
  5. 根据权利要求1-4中任一项所述的多孔碳纳米管微球材料，其中所述碳纳米管微球材料的比表面积为100～1500m2/g。
  6. 根据权利要求1-5中任一项所述的多孔碳纳米管微球材料，其中所述碳纳米管微球所含孔隙的孔径为1nm～200nm。
  7. 根据权利要求1-6中任一项所述的多孔碳纳米管微球材料，其中所述碳纳米管包括多壁碳纳米管、双壁碳纳米管和单壁碳纳米管中的任意一种或两种以上的组合。
  8. 根据权利要求1-7中任一项所述的多孔碳纳米管微球材料，其中所述碳纳米管包括商品化碳纳米管、纯化碳纳米管和经过表面功能化处理的碳纳米管中的任意一种或两种以上的组合。
  9. 一种制备如权利要求1-8中任一项所述的多孔碳纳米管微球材料的方法，包括：将碳纳米管分散于溶剂中形成分散液后喷雾干燥，从而制得所述碳纳米管微球材料。
  10. 根据权利要求9所述的方法，其中所述分散在没有表面活性剂的情况下进行。
  11. 根据权利要求9或10所述的方法，其中所述喷雾干燥的条件包括：进 风温度为150～250℃，出风温度为90℃以上。
  12. 根据权利要求9-11中任一项所述的方法，其中喷雾干燥的条件包括：喷雾速度为1毫升/分钟至100升/分钟。
  13. 根据权利要求9-12中任一项所述的方法，其中所述分散液包含浓度为10～50g/L的碳纳米管。
  14. 权利要求1-8中任一项所述的多孔碳纳米管微球材料在制备电池或超级电容器中的应用，所述电池包括锂硫电池或燃料电池。
  15. 一种电极材料，其包含权利要求1-8中任一项所述的多孔碳纳米管微球材料或通过权利要求9-13中任一项所述的方法制备的多孔碳纳米管微球材料。
  16. 一种金属锂-骨架碳复合材料，包括多孔碳材料载体以及形成于所述碳材料载体孔隙中的金属锂。
  17. 根据权利要求16所述的金属锂-骨架碳复合材料，其中所述多孔碳材料包括碳纤维微球、多孔碳纳米管微球和乙炔黑。
  18. 根据权利要求17所述的金属锂-骨架碳复合材料，其中所述多孔碳纳米管微球为权利要求1-8中任一项所述的多孔碳纳米管微球材料。
  19. 根据权利要求18所述的金属锂-骨架碳复合材料，其中所述多孔碳纳米管微球的平均孔径在10～50nm之间。
  20. 一种电池负极，其负极材料为权利要求16至19任一项所述的金属锂-骨架碳复合材料。
  21. 一种电池，其包括权利要求20所述的负极。
  22. 根据权利要求21所述的电池，其中所述电池为二次电池，所述二次电池为锂-硫电池、金属锂-氧化物电池、金属锂-聚合物电池或可充电锂离子电池。
  23. 一种金属-骨架碳复合材料的制备方法，包括：将熔融状态的金属与多孔碳材料载体混合均匀，冷却获得金属-骨架碳复合材料。
  24. 根据权利要求23所述的金属-骨架碳复合材料的制备方法，其中所述金属包括锂、钠和钾。
  25. 根据权利要求23所述的金属-骨架碳复合材料的制备方法，其中所述多孔碳材料载体包括碳纤维微球、多孔碳纳米管微球和乙炔黑。
  26. 根据权利要求25所述的金属-骨架碳复合材料的制备方法，其中所述碳 材料载体为权利要求1-8中任一项所述的多孔碳纳米管微球材料或通过权利要求9-13中任一项所述的方法制备的多孔碳纳米管微球材料。
PCT/CN2015/074733 2014-03-21 2015-03-20 多孔碳纳米管微球及其制备方法与应用、金属锂-骨架碳复合材料及其制备方法、负极和电池 WO2015139660A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP15765300.7A EP3133047B8 (en) 2014-03-21 2015-03-20 Lithium metal-skeleton carbon composite and preparation method therefor, negative electrode, and battery
KR1020167029453A KR101900780B1 (ko) 2014-03-21 2015-03-20 다공성 탄소 나노튜브 마이크로스피어, 이의 제조방법 및 이의 용도, 리튬 금속-골격 탄소 복합 재료 및 이의 제조방법, 음극, 및 전지
US15/127,809 US10868298B2 (en) 2014-03-21 2015-03-20 Porous carbon nanotube microsphere and preparation method and use thereof, lithium metal-skeleton carbon composite and preparation method thereof, negative electrode, and battery
JP2016558783A JP6445585B2 (ja) 2014-03-21 2015-03-20 多孔質カーボンナノチューブミクロスフェア及びその製造方法と使用、金属リチウム‐骨格炭素複合材料及びその製造方法、負極、及び電池

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201410106376.0A CN104925778B (zh) 2014-03-21 2014-03-21 碳纳米管微球及其制备方法与应用
CN201410106376.0 2014-03-21
CN201410395114.0 2014-08-13
CN201410395114.0A CN105374991B (zh) 2014-08-13 2014-08-13 金属锂-骨架碳复合材料及其制备方法、负极和二次电池

Publications (1)

Publication Number Publication Date
WO2015139660A1 true WO2015139660A1 (zh) 2015-09-24

Family

ID=54143768

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/074733 WO2015139660A1 (zh) 2014-03-21 2015-03-20 多孔碳纳米管微球及其制备方法与应用、金属锂-骨架碳复合材料及其制备方法、负极和电池

Country Status (5)

Country Link
US (1) US10868298B2 (zh)
EP (1) EP3133047B8 (zh)
JP (1) JP6445585B2 (zh)
KR (1) KR101900780B1 (zh)
WO (1) WO2015139660A1 (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019019410A1 (zh) * 2017-07-26 2019-01-31 中能中科（天津）新能源科技有限公司 改性无锂负极、其制备方法和含有其的锂离子电池
JP2019512157A (ja) * 2016-02-23 2019-05-09 マックスウェル テクノロジーズ インコーポレイテッド エネルギー貯蔵装置のための元素金属および炭素の混合物
JP2019513673A (ja) * 2017-03-07 2019-05-30 エルジー・ケム・リミテッド 炭素−硫黄複合体、この製造方法、これを含む正極及びリチウム−硫黄電池
US11462741B2 (en) * 2017-07-26 2022-10-04 China Energy Cas Technology Co., Ltd. Metallic lithium-skeleton carbon composite material having a hydrophobic cladding layer, preparation method and use thereof
US11866332B2 (en) 2017-07-26 2024-01-09 China Energy Cas Technology Co., Ltd. Carbon nanoparticle-porous skeleton composite material, its composite with lithium metal, and their preparation methods and use
US11888108B2 (en) 2017-02-21 2024-01-30 Tesla, Inc. Prelithiated hybridized energy storage device

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107225251A (zh) * 2017-07-25 2017-10-03 天津中能锂业有限公司 一种钝化锂微球生产装置
KR102244906B1 (ko) * 2017-09-28 2021-04-26 주식회사 엘지화학 티타니아-탄소나노튜브-황(TiO2-x-CNT-S) 복합체 및 그의 제조방법
CN109686898B (zh) * 2017-10-18 2020-08-11 清华大学 锂硫电池隔膜
CN109686897B (zh) * 2017-10-18 2020-08-11 清华大学 锂硫电池隔膜
CN109686906B (zh) * 2017-10-18 2020-08-11 清华大学 锂硫电池
CN109686899B (zh) * 2017-10-18 2020-08-11 清华大学 锂硫电池
EP3476818A1 (en) * 2017-10-27 2019-05-01 Heraeus Battery Technology GmbH A process for the preparation of a porous carbon material using an improved carbon source
EP3476817A1 (en) 2017-10-27 2019-05-01 Heraeus Battery Technology GmbH A process for the preparation of a porous carbon material using an improved amphiphilic species
KR102346840B1 (ko) 2017-11-08 2022-01-03 주식회사 엘지에너지솔루션 다공성 탄소, 이를 포함하는 양극 및 리튬-황 이차전지
US11462740B2 (en) * 2017-11-30 2022-10-04 Zeon Corporation Conductive material paste for electrochemical device, slurry composition for electrochemical device positive electrode and method of producing same, positive electrode for electrochemical device, and electrochemical device
KR20200138250A (ko) * 2018-03-02 2020-12-09 아줄 에너지 인크. 촉매, 액상조성물, 전극, 전기화학반응용 촉매전극, 연료전지 및 공기전지
KR102065644B1 (ko) * 2018-04-04 2020-01-13 주식회사 디알비동일 리튬금속카본복합체 및 이의 제조방법
CN108923036A (zh) * 2018-07-17 2018-11-30 浙江大学山东工业技术研究院 碳-锂复合粉末及其制备方法、锂金属二次电池电极的制备方法
US10836952B2 (en) 2018-08-14 2020-11-17 King Fahd University Of Petroleum And Minerals Oil recovery methods using carboxylated pyrolyzed date leaves
KR102343176B1 (ko) * 2019-01-21 2021-12-27 주식회사 엘지에너지솔루션 리튬 복합 음극 활물질, 이를 포함하는 음극 및 이들의 제조방법
KR102233923B1 (ko) * 2019-08-29 2021-03-29 서강대학교 산학협력단 표면 선택적 금속산화물-탄소나노튜브 복합체, 이를 포함하는 리튬-황 전지, 그리고 그 제조 방법
CN112447410B (zh) * 2019-09-03 2022-05-06 黑龙江大学 磷酸铁锂/碳纳米管微球正极材料的制备方法、正极材料及水系锂离子电容器的优化方法
CN112909250B (zh) * 2019-11-19 2022-04-26 中能中科（天津）新能源科技有限公司 碳材料微球、锂碳粉及其制备方法和应用
CN111162265B (zh) * 2020-01-17 2022-04-12 中国人民解放军国防科技大学 一种用于固态电池的金属锂复合负极的制备方法
CN111755261A (zh) * 2020-07-09 2020-10-09 浙江奚态生物科技有限公司 一种掺银纳米线的纳米碳球电极材料的制备方法
WO2022019622A1 (ko) * 2020-07-23 2022-01-27 주식회사 엘지에너지솔루션 리튬 이차 전지용 음극, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지
JPWO2022118562A1 (zh) 2020-12-04 2022-06-09
CN114400302B (zh) * 2021-02-10 2023-05-09 北京卫蓝新能源科技有限公司 多孔碳微球及其制备方法碳锂复合材料、负极和锂金属电池
CN113036100B (zh) * 2021-02-25 2022-04-29 浙江大学 一种含刚性颗粒骨架的锂金属复合负极及其制备方法
US11417877B1 (en) 2021-04-14 2022-08-16 Guangdong University Of Technology Carbon quantum dot/carbon coated VSe2 composite material (VSe2@CQD) for potassium ion battery and preparation method thereof
CN114335540B (zh) * 2021-12-29 2023-03-21 北京卫蓝新能源科技有限公司 一种亲锂碳骨架复合材料及其制备方法和应用
CN115020657B (zh) * 2022-07-27 2024-01-30 西安交通大学 一种碱金属复合负极及其一体化制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101567437A (zh) * 2009-04-24 2009-10-28 厦门大学 一种有序介孔炭-硫纳米复合正极材料及其制备方法
CN101607704A (zh) * 2009-07-14 2009-12-23 清华大学 一种碳纳米管绵及其制备方法
CN102891306A (zh) * 2012-10-23 2013-01-23 中国科学院过程工程研究所 一种锂离子电池Si/Li4Ti5O12/CNT复合负极材料及其制备方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7531267B2 (en) * 2003-06-02 2009-05-12 Kh Chemicals Co., Ltd. Process for preparing carbon nanotube electrode comprising sulfur or metal nanoparticles as a binder
US20050130043A1 (en) * 2003-07-29 2005-06-16 Yuan Gao Lithium metal dispersion in electrodes
US20070190422A1 (en) * 2006-02-15 2007-08-16 Fmc Corporation Carbon nanotube lithium metal powder battery
KR20100038094A (ko) * 2007-07-11 2010-04-12 미꾸니 시끼소 가부시키가이샤 카본나노튜브의 조립물 및 이의 제조 방법
CN101239713A (zh) 2008-03-04 2008-08-13 江苏大学 一种以聚合物为原料生产多壁碳纳米管的方法
KR101198307B1 (ko) * 2009-08-18 2012-11-07 한국전기연구원 탄소나노튜브 마이크로볼의 제조방법, 이에 의해 제조된 탄소나노튜브 마이크로볼 및 이를 이용한 전극의 제조방법
KR101043273B1 (ko) * 2011-01-19 2011-06-21 주식회사 한나노텍 열가소성 수지층으로 둘러싸인 탄소나노튜브 마이크로캡슐을 포함하는 전도성 고분자 충전제 및 그 제조방법
US20140227522A1 (en) * 2011-09-09 2014-08-14 Sumitomo Bakelite Company Limited Carbon material for lithium ion secondary battery, negative electrode material for lithium ion secondary battery and lithium ion secondary battery
JP5831110B2 (ja) * 2011-09-30 2015-12-09 住友ベークライト株式会社 リチウムイオン二次電池用炭素材、リチウムイオン二次電池用負極材およびリチウムイオン二次電池
CN102515152B (zh) 2011-12-23 2013-04-24 深圳市贝特瑞纳米科技有限公司 制备球状石墨烯的方法
GB2500611A (en) * 2012-03-26 2013-10-02 Cambridge Entpr Ltd Powder comprising carbon nanostructures and method of preparation
US20130264524A1 (en) * 2012-04-05 2013-10-10 Kang-Yu LIU Electrode and fabrication method thereof
CN103214245B (zh) 2013-03-29 2014-11-05 中国科学院过程工程研究所 一种碳/碳复合微球材料、生产方法及锂离子电池
US9882238B2 (en) * 2013-05-16 2018-01-30 Nanotek Instruments, Inc. Lithium-sulfur secondary battery containing gradient electrolyte
US9059481B2 (en) * 2013-08-30 2015-06-16 Nanotek Instruments, Inc. Non-flammable quasi-solid electrolyte and non-lithium alkali metal or alkali-ion secondary batteries containing same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101567437A (zh) * 2009-04-24 2009-10-28 厦门大学 一种有序介孔炭-硫纳米复合正极材料及其制备方法
CN101607704A (zh) * 2009-07-14 2009-12-23 清华大学 一种碳纳米管绵及其制备方法
CN102891306A (zh) * 2012-10-23 2013-01-23 中国科学院过程工程研究所 一种锂离子电池Si/Li4Ti5O12/CNT复合负极材料及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YI, HAIXIA: "Preparation and Application Research of Carbon Nanotube Capsules", SCIENCE -ENGINEERING (A), CHINA MASTER'S THESES FULL-TEXT DATABASE, 15 December 2007 (2007-12-15), pages 15, XP008184973 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019512157A (ja) * 2016-02-23 2019-05-09 マックスウェル テクノロジーズ インコーポレイテッド エネルギー貯蔵装置のための元素金属および炭素の混合物
US11527747B2 (en) 2016-02-23 2022-12-13 Tesla, Inc. Elemental metal and carbon mixtures for energy storage devices
JP7227766B2 (ja) 2016-02-23 2023-02-22 テスラ・インコーポレーテッド エネルギー貯蔵装置のための元素金属および炭素の混合物
US11901549B2 (en) 2016-02-23 2024-02-13 Tesla, Inc. Elemental metal and carbon mixtures for energy storage devices
US11888108B2 (en) 2017-02-21 2024-01-30 Tesla, Inc. Prelithiated hybridized energy storage device
JP2019513673A (ja) * 2017-03-07 2019-05-30 エルジー・ケム・リミテッド 炭素−硫黄複合体、この製造方法、これを含む正極及びリチウム−硫黄電池
US11038194B2 (en) 2017-03-07 2021-06-15 Lg Chem, Ltd. Carbon-sulfur complex, method for producing same, and cathode and lithium-sulfur battery comprising same
WO2019019410A1 (zh) * 2017-07-26 2019-01-31 中能中科（天津）新能源科技有限公司 改性无锂负极、其制备方法和含有其的锂离子电池
US11462741B2 (en) * 2017-07-26 2022-10-04 China Energy Cas Technology Co., Ltd. Metallic lithium-skeleton carbon composite material having a hydrophobic cladding layer, preparation method and use thereof
US11866332B2 (en) 2017-07-26 2024-01-09 China Energy Cas Technology Co., Ltd. Carbon nanoparticle-porous skeleton composite material, its composite with lithium metal, and their preparation methods and use

Also Published As

Publication number Publication date
KR101900780B1 (ko) 2018-09-20
EP3133047A4 (en) 2017-10-25
EP3133047B1 (en) 2020-06-03
EP3133047A1 (en) 2017-02-22
JP6445585B2 (ja) 2018-12-26
EP3133047B8 (en) 2020-07-22
JP2017517467A (ja) 2017-06-29
US10868298B2 (en) 2020-12-15
KR20160145605A (ko) 2016-12-20
US20170110719A1 (en) 2017-04-20

Similar Documents

Publication Publication Date Title
WO2015139660A1 (zh) 多孔碳纳米管微球及其制备方法与应用、金属锂-骨架碳复合材料及其制备方法、负极和电池
US11866332B2 (en) Carbon nanoparticle-porous skeleton composite material, its composite with lithium metal, and their preparation methods and use
CN105374991B (zh) 金属锂-骨架碳复合材料及其制备方法、负极和二次电池
Kim et al. Controlled Ag-driven superior rate-capability of Li 4 Ti 5 O 12 anodes for lithium rechargeable batteries
US20150162617A1 (en) Si@C core/shell Nanomaterials for High Performance Anode of Lithium Ion Batteries
Zou et al. Microwave-assisted preparation of hollow porous carbon spheres and as anode of lithium-ion batteries
CN107221654B (zh) 一种三维多孔鸟巢状硅碳复合负极材料及其制备方法
CN107808955B (zh) 一种具有球形结构的活性炭材料及其制备方法和应用
WO2021129125A1 (zh) 一种中空核壳结构硅碳复合负极材料及其制备方法
WO2019019410A1 (zh) 改性无锂负极、其制备方法和含有其的锂离子电池
Qian et al. High rate lithium-sulfur batteries enabled by mesoporous TiO2 nanotubes prepared by electrospinning
WO2022121281A1 (zh) 一种自填充包覆硅基复合材料、其制备方法及其应用
CN103346302A (zh) 一种锂电池硅碳纳米管复合负极材料及其制备方法与应用
WO2022021933A1 (zh) 非水电解质二次电池用负极材料及其制备方法
Jin et al. Pomegranate-like Li3VO4/3D graphene networks nanocomposite as lithium ion battery anode with long cycle life and high-rate capability
CN106997947A (zh) 一种自组装聚酰亚胺多孔材料、制备方法及其在锂硫电池的应用
Zhang et al. A novel carbon nanotubes@ porous carbon/sulfur composite as efficient electrode material for high-performance lithium-sulfur battery
Wang et al. Carbon-coated SnO2@ carbon nanofibers produced by electrospinning-electrospraying method for anode materials of lithium-ion batteries
Liu et al. Blended spherical lithium iron phosphate cathodes for high energy density lithium–ion batteries
CN108232153B (zh) 一种锂离子电池用含镍层状正极材料/碳复合材料及其制备方法
Zhang et al. Shaddock wadding created activated carbon as high sulfur content encapsulator for lithium-sulfur batteries
WO2022121280A1 (zh) 一种类石榴结构硅基复合材料、其制备方法及其应用
CN108565125A (zh) 预锂化锂离子超级电容器负极、其制备方法和锂离子超级电容器
Xue et al. Fabrication and performance of Li 4 Ti 5 O 12/cotton-driven carbon fiber as anode for lithium-ion batteries
CN113471405A (zh) 预锂化负极、其制备方法和含预锂化负极的锂离子电池和超级电容器

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: 15765300

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016558783

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 15127809

Country of ref document: US

REEP Request for entry into the european phase

Ref document number: 2015765300

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2015765300

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20167029453

Country of ref document: KR

Kind code of ref document: A