CN106711422A - Co3C@onion-shaped carbon/amorphous carbon nano-composite as well as preparation method and application thereof - Google Patents

Co3C@onion-shaped carbon/amorphous carbon nano-composite as well as preparation method and application thereof Download PDF

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CN106711422A
CN106711422A CN201710017966.XA CN201710017966A CN106711422A CN 106711422 A CN106711422 A CN 106711422A CN 201710017966 A CN201710017966 A CN 201710017966A CN 106711422 A CN106711422 A CN 106711422A
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nano
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amorphous carbon
onion
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刘先国
李振兴
孙玉萍
晋传贵
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Anhui University of Technology AHUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M4/58—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
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    • 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
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention provides a Co3C@onion-shaped carbon/amorphous carbon nano-composite as well as a preparation method and application thereof and belongs to the technical field of preparation of nanomaterials. The microstructure of the nanocomposite material is formed by embedding a Co3C@onion-shaped carbon core-shell structure nanocapsule into an amorphous carbon nanosheet. The preparation method comprises the following steps: pressing cobalt powder and coal dust into a block body to serve as an anode target material according to a certain atomic percent by adopting a plasma arc discharge method; using graphite as a cathode material, introducing argon and hydrogen as working gases, and keeping a certain distance between a cathode graphite electrode and the anode target material cobalt-coal dust block body; carrying out arc discharge between an anode and a cathode, thus obtaining the Co3C@onion-shaped carbon/amorphous carbon nano-composite. When the nanocomposite is used as an anode of a lithium ion battery, the nanocomposite shows good cycle performance and is a promising anode material of the lithium ion battery. The preparation method disclosed by the invention has the advantages of simple preparation process, low cost and easiness for industrial production.

Description

A kind of Co3C@onions shapes carbon/amorphous carbon nano-complex and preparation method thereof and Using
Technical field
The invention belongs to technical field of material, and in particular to a kind of Co3C@onions shapes carbon/amorphous carbon is nano combined Thing and its preparation method and application.
Background technology
As people are growing to the demand of the energy, the aggravation of fossil fuel reserves reductions and environmental pollution, open The novel energy for sending out clean and effective turns into focus of concern.Lithium ion battery as a kind of energy storing device, with its ring The features such as guarantor, light, high power capacity, long-life, is widely used in small portable device.Lithium ion battery plus-negative plate material is Determine the central factor of its performance.Current commercialized negative material is mainly graphite material, and its theoretical specific capacity only has 372mAh/g, can not meet demand of the people to battery performance.Therefore, novel cathode material for lithium ion battery is researched and developed It is significant.
Although transition metal carbides possess the advantages such as nontoxic, rich reserves, inexpensive and excellent catalytic performance, but Because it has less specific capacity in theory, transition metal carbides are not used as the negative pole material of lithium ion battery for a long time Material.2012, Su et al first reported core shell structure Fe@Fe3Discharge capacity of the C/C nano-complexes with stabilization~ 500mAh/g, demonstrates its potentiality as lithium ion battery negative material.Although, Fe and Fe3C is for Li+Intercalation is almost without work Property, but author points out Fe3C can promote the formation/decomposable process of solid electrolyte interface (SEI) film reversible as catalyst, So as to improve the chemical property of carbon based negative electrodes.(L.Su,Z.Zhou,P.Shen.Core-shell Fe@Fe3C/C nanocomposites as anode materials for Li ion batteries.Electrochimica Acta 87 (2013)180-185).It is well known that hindering carbide as lithium ion battery negative material, also following two obstacles：(1) Volumetric expansion/contraction during repetitive cycling；(2) low electric conductivity of carbide.Currently for grinding for two above problem Study carefully, be broadly divided into three kinds of approach and solve：(1) nanosizing of material；(2) Composite of active material；(3) nano composite material. Wherein the third approach is most widely used under study for action, wherein in the selection of base material, due to carbon material Stability Analysis of Structures, in charge and discharge Volume Changes are relatively small in electric process, and electric conductivity and heat, chemical stability are good, with certain specific capacity, therefore receive Extensive concern is arrived.Under normal circumstances, the carbon component in nano-complex has dual-use function：Promote carbon as conductive additive The electron transport of compound and as elastic cord breaker strengthen electrode structure stability.
Lot of domestic and international scholar is devoted to the preparation method research of transition metal carbides/carbon composite, and brief introduction is such as Under：
Chinese invention patent " carbon covered metal, the synthetic method of carbon covered metal carbide nanometer micro mist " (patent No.: CN99120144.2 AC arc discharge method) is used, is put by plasma in vaccum consumable electrode electric arc furnace using carbon and metal Electricity evaporates simultaneously, through chemical reaction generation carbon covered metal or metal carbides nano powder.
Chinese invention patent " comprising carbon composite of metal carbide particles being dispersed therein and preparation method thereof " (the patent No.:200580012680.8) be related to carbon composite, the carbon composite comprising be dispersed in carbon, carbon fiber or carbon/ Metal carbide particles in carbon fiber substrate and without free metal particle, wherein metal carbide particles are at least particle table Face or whole particle are metal carbides, by source metal (i.e. selected from metallic particles, metal oxide particle or composition metal oxygen At least one in compound particle) and carbon source (i.e. thermosetting resin) synthesize in the original location.
A kind of Chinese invention patent " charcoal Base Metal nitride, the preparation method of carbide electrochemical capacitance material " (patent No.： 200710022253.9) raw material are obtained into hydrogel precursor by gel reaction, gained hydrogel is in nitriding gas or hydrogen Through constant pressure and dry and carbonization under gas effect, charcoal base transition metal nitride, carbide electrochemical capacitance material is obtained.
A kind of Chinese invention patent " C/Fe3C lithium ion battery negative materials and preparation method thereof " (patent No.: 201010532415.5) to raw material using thermal polymerization in organic solvent, precursor is obtained, then under argon gas atmosphere protection, It is heat-treated, is obtained C/Fe3C compounds, it is by amorphous carbon and Fe3C is constituted.
Chinese invention patent " preparation method of onion carbon carrying transition metal carbide nanometer compound " (patent No.: 201010600970.7) raw material are fitted into closed reactor in proportion, by heating response kettle, are aided in using initiator Chemical vapour deposition technique single step reaction obtain the nano-complex of onion carbon carrying transition metal carbide.
A kind of Chinese invention patent " method for preparing metal carbides or carbon-clad metal carbide " (patent No.： 201210562395.5) metal salt powder is formed into metallic oxide precursor thing in high-temperature roasting, is made with liquid carbon compound Metal carbides or carbon-clad metal carbon are prepared for liquid carbon source and metallic oxide precursor thing carry out reduction and carburizing reagent Compound.
Chinese invention patent " Macro film being made up of Nano capsule and nanotube and fiber absorbing material and its preparation side The method " (patent No.:Plasma arc discharge technology 201310065805.X) is utilized, is prepared for by Fe@C, Fe3C@C nano glue Capsule and CNT are interweaved the Macro film for connecting and composing.
Chinese invention patent " a kind of cobalt tungsten bimetallic carbide of carbon coating, preparation method and applications " (patent No.： 201410723029.2) it is that can obtain carbon by the mixture of one-step calcination cobalt, two kinds of metallic compounds of tungsten and nitrogen-rich organic thing The cobalt tungsten bimetallic carbide of cladding.
A kind of Chinese invention patent " tubulose core shell structure graphitie@Fe3Composite of C and preparation method thereof and should With " (the patent No.：201410827354.3) with graphite worm, ferrocene, 30% hydrogen peroxide as raw material, by simple liquid phase side Method is simultaneously sintered under inert gas shielding, has prepared graphite@Fe3C nano compound.
Since it is desired that high temperature, using poisonous and expensive chemical precursor, advanced equipment and dull flow, the above Transition metal carbide/C compound preparation methods are generally difficult to industrialized.According to application demand, people generally wish to obtain Obtain process is simple, the transition metal carbide/C nano compound of low cost.However, through retrieval, Co3C@onions shapes carbon/nothing is fixed The method that shape carbon nano-composite material and a step prepare this kind of nano composite material has not been reported.
The content of the invention
It is an object of the invention to provide a kind of Co3C@onions shapes carbon/amorphous carbon nano-complex and preparation method thereof, with The good preparation process simultaneously of cycle performance is simple when the nano-complex that phase obtains is as lithium ion battery negative, low cost.
To achieve these goals, the present invention is achieved by the following technical programs.
The present invention prepares a kind of Co3C@onions shapes carbon/amorphous carbon nano-complex, the nano-complex microstructure is Co3C@onion shape carbon nuclear shell structure nanos capsule is embedded in amorphous carbon nanometer sheet.Wherein, Co3The grain of C@onion shape carbon Nano capsules Footpath is 2~15nm, and kernel is Co3C nano particle, shell is onion shape carbon.
Present invention also offers above-mentioned Co3The preparation method of C@onions shapes carbon/amorphous carbon nano-complex, the material is Using plasma arc discharge technology, original position prepares under working gas；Wherein：
It is negative electrode to use graphite electrode, and cobalt-coal powdered block is anode target material, negative electrode graphite electrode and anode target material cobalt- The distance of 2~30mm is kept between coal powdered block；The voltage of arc discharge is 10~40V；Working gas is argon gas and hydrogen Gas.
The anode target material is cobalt-coal powdered block, and cobalt powder and coal dust are pressed into block under pressure 1MPa~1GPa As the anode target material material of plasma arc furnace, mass percent in the anode target material material shared by cobalt for 30~ 50%.
The partial pressure of the argon working gas is 0.01~0.5MPa, and the partial pressure of hydrogen gas is 0.01~0.3MPa.
Present invention also offers Co3C@onions shapes carbon/amorphous carbon nano-complex is used as lithium ion battery negative material Application.
The method of the application is：(1) according to mass ratio 7:2:1 ratio weighs Co3C@onions shapes carbon/amorphous carbon is received Rice compound, acetylene black, segregation PVF, are put into grinding in crucible, are subsequently adding 1-METHYLPYRROLIDONE and continue grinding, make In the pasty state, then uniformly be applied on Copper Foil for it by mixture, in 100 DEG C or so dry 12~20h, afterwards carries out this Copper Foil Roll, be cut into the certain disk of diameter, be made electrode slice；(2) in the glove box full of argon gas, in conventional manner by electrode Piece, barrier film, lithium piece and nickel foam are assembled into button battery.
Constant current charge-discharge loop test, the circulation of the button battery that measure is made are carried out with test method at room temperature Stability.
Compared with the prior art, it is of the invention to have the prominent advantages that
1) present invention has prepared Co first3C@onions shapes carbon/amorphous carbon nano-complex；
2) preparation process condition of the present invention is simple, and low cost, it is easy to control disposably generates product, is Co3C@onion shapes The practical application of carbon/amorphous carbon nano-complex provides condition；
3) the prepared Co of the present invention3C@onions shapes carbon/amorphous carbon nano-complex is with Co3C@onion shape carbon nucleocapsid knots In structure Nano capsule insertion amorphous carbon nanometer sheet, the structure is conducive to the diffusion of lithium ion, buffer volumes change and electrical conductivity Raising, and Co3C nano particle has the effect of catalytic modification SEI films so that the partial reduction products of SEI films are reversible, because This is conducive to the chemical property of nano composite material, is particularly conducive to its cyclical stability.
Brief description of the drawings
Fig. 1 is preparation Co of the present invention3The schematic device of C@onions shapes carbon/amorphous carbon nano-complex；
Label in figure：1st, upper lid；2nd, negative electrode；3rd, valve；4th, anode target material；5th, observation window；6th, baffle plate；7th, copper anode；8th, press from both sides Head；9th, graphite crucible；10th, DC pulse power supply；A, cooling water；B, argon gas；C, hydrogen.
Fig. 2 is Co prepared by the embodiment of the present invention 13The X-ray diffraction of C@onions shapes carbon/amorphous carbon nano-complex (XRD) collection of illustrative plates；
According to JCPDS PDF cards, nano-complex principal phase can be retrieved for Co3C crystalline phases are constituted.2θ≈20oThe width at place Peak is the characteristic peak of amorphous carbon, because onion shape carbon is in shell, so XRD cannot detect onion shape carbon phase.
Fig. 3 is Co prepared by the embodiment of the present invention 13The transmitted electron of C@onions shapes carbon/amorphous carbon nano-complex shows Micro mirror (TEM) image；
As can be seen from the figure Co3C@onion shape carbon Nano capsules are distributed in amorphous carbon nanometer sheet, its Nano capsule Particle diameter be 2~15nm.
Fig. 4 is the Co prepared by the embodiment of the present invention 13The high-resolution of C@onions shapes carbon/amorphous carbon nano-complex is saturating Penetrate electron microscope image；
As can be seen from the figure Co obtained by3C@onions shapes carbon/amorphous carbon nano-complex is Co3C@onion shapes carbon nanometer In capsule insertion amorphous carbon nanometer sheet, wherein, Co3C@onion shape carbon Nano capsules kernel is Co3C nano particle, shell is ocean Green onion shape carbon.
Fig. 5 is the Co of preparation in the embodiment of the present invention 13C@onions shapes carbon/amorphous carbon nano-complex is used as negative pole material The circulation discharge curve of material；
As seen from the figure, charge and discharge cycles test is carried out with the electric current of 100mA/g, circulating the discharge capacity after 100 times is 939mAh/g。
Fig. 6 is the Co of preparation in the embodiment of the present invention 23C@onions shapes carbon/amorphous carbon nano-complex is used as negative pole material The circulation discharge curve of material；
As seen from the figure, charge and discharge cycles test is carried out with the electric current of 100mA/g, circulating the discharge capacity after 100 times is 936mAh/g。
Specific embodiment
With reference to embodiment, the invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
Lid 1 on device shown in Fig. 1 is opened, making negative electrode 2 with graphite is fixed on chuck 8, institute consumable anode target 4 Composition is pure cobalt powder and coal dust (mass ratio 50:50) block being pressed into, is placed on the copper anode 7 of logical cooling water, in logical cooling water Copper anode and target between be graphite crucible 9.Kept between negative electrode graphite electrode and 4 anode target materials cobalt-coal powdered block The distance of 30mm.Lid 1 on lid mounted device, leads to cooling water a, whole operating room is vacuumized by valve 3 after, is passed through argon gas b and hydrogen Gas c, the partial pressure of argon gas is 0.5MPa, and the partial pressure of hydrogen is 0.3MPa, connects DC pulse power supply 10, and voltage is 40V.Arc light is put Adjustment work electric current keeps relative stability with voltage in electric process.Co is obtained3C@onions shapes carbon/amorphous carbon nano-complex, The nano-complex microstructure is Co3In C@onion shape carbon nuclear shell structure nanos capsule insertion amorphous carbon nanometer sheet, wherein Co3The particle diameter of C@onion shape carbon Nano capsules is 2~15nm, and kernel is Co3C nano particle, shell be onion shape carbon, such as Fig. 3, Shown in Fig. 4.
According to mass ratio 7:2:1 ratio weighs Co3C@onions shapes carbon/amorphous carbon nano-complex, acetylene black, segregation PVF, is put into grinding in crucible, is subsequently adding 1-METHYLPYRROLIDONE and continues grinding, makes mixture in the pasty state, then will It is uniformly applied on Copper Foil, and 12h is dried at 100 DEG C or so, is afterwards rolled this Copper Foil, is cut into the certain circle of diameter Piece, is made electrode slice；In the glove box full of argon gas, electrode slice, barrier film, lithium piece and nickel foam are assembled into conventional manner Button battery.At room temperature, constant current charge-discharge loop test is carried out with 100mA/g, after being circulated at 100 times, its capacitance It is 939mAh/g, this explanation of such as Fig. 5 Co3C@onions shapes carbon/amorphous carbon nano-complex is used as lithium ion battery negative material With good cycle performance.
Embodiment 2
Lid 1 on device shown in Fig. 1 is opened, making negative electrode 2 with graphite is fixed on chuck 8, institute consumable anode target 4 Composition is pure cobalt powder and coal dust (mass ratio 30:70) block being pressed into, is placed on the copper anode 7 of logical cooling water, in logical cooling water Copper anode and target between be graphite crucible 9.Kept between negative electrode graphite electrode and 4 anode target materials cobalt-coal powdered block The distance of 20mm.Lid 1 on lid mounted device, leads to cooling water a, whole operating room is vacuumized by valve 3 after, is passed through argon gas b and hydrogen Gas c, the partial pressure of argon gas is 0.5MPa, and the partial pressure of hydrogen is 0.3MPa, connects DC pulse power supply 10, and voltage is 10V.Arc light is put Adjustment work electric current keeps relative stability with voltage in electric process.Co is obtained3C@onions shapes carbon/amorphous carbon nano-complex, The nano-complex microstructure is Co3In C@onion shape carbon nuclear shell structure nanos capsule insertion amorphous carbon nanometer sheet.Wherein Co3The particle diameter of C@onion shape carbon Nano capsules is 2~15nm, and kernel is Co3C nano particle, shell is onion shape carbon.
According to mass ratio 7:2:1 ratio weighs Co3C@onions shapes carbon/amorphous carbon nano-complex, acetylene black, segregation PVF, is put into grinding in crucible, is subsequently adding 1-METHYLPYRROLIDONE and continues grinding, makes mixture in the pasty state, then will It is uniformly applied on Copper Foil, and 20h is dried at 100 DEG C or so, is afterwards rolled this Copper Foil, is cut into the certain circle of diameter Piece, is made electrode slice；In the glove box full of argon gas, electrode slice, barrier film, lithium piece and nickel foam are assembled into conventional manner Button battery.At room temperature, constant current charge-discharge loop test is carried out with 100mA/g, after being circulated at 100 times, its capacitance It is 936mAh/g, this explanation of such as Fig. 6 Co3C@onions shapes carbon/amorphous carbon nano-complex is used as lithium ion battery negative material With good cycle performance.
Embodiment 3
Lid 1 on device shown in Fig. 1 is opened, making negative electrode 2 with graphite is fixed on chuck 8, institute consumable anode target 4 Composition is pure cobalt powder and coal dust (mass ratio 50:50) block being pressed into, is placed on the copper anode 7 of logical cooling water, in logical cooling water Copper anode and target between be graphite crucible 9.Kept between negative electrode graphite electrode and 4 anode target materials cobalt-coal powdered block The distance of 30mm.Lid 1 on lid mounted device, leads to cooling water a, whole operating room is vacuumized by valve 3 after, is passed through argon gas b and hydrogen Gas c, the partial pressure of argon gas is 0.5MPa, and the partial pressure of hydrogen is 0.3MPa, connects DC pulse power supply 10, and voltage is 20V.Arc light is put Adjustment work electric current keeps relative stability with voltage in electric process.Co is obtained3C@onions shapes carbon/amorphous carbon nano-complex, The nano-complex microstructure is Co3In C@onion shape carbon nuclear shell structure nanos capsule insertion amorphous carbon nanometer sheet.Wherein Co3The particle diameter of C@onion shape carbon Nano capsules is 2~15nm, and kernel is Co3C nano particle, shell is onion shape carbon.
Embodiment 4
Lid 1 on device shown in Fig. 1 is opened, making negative electrode 2 with graphite is fixed on chuck 8, institute consumable anode target 4 Composition is pure cobalt powder and coal dust (mass ratio 40:60) block being pressed into, is placed on the copper anode 7 of logical cooling water, in logical cooling water Copper anode and target between be graphite crucible 9.Kept between negative electrode graphite electrode and 4 anode target materials cobalt-coal powdered block The distance of 20mm.Lid 1 on lid mounted device, leads to cooling water a, whole operating room is vacuumized by valve 3 after, is passed through argon gas b and hydrogen Gas c, the partial pressure of argon gas is 0.2MPa, and the partial pressure of hydrogen is 0.2MPa, connects DC pulse power supply 10, and voltage is 30V.Arc light is put Adjustment work electric current keeps relative stability with voltage in electric process.Co is obtained3C@onions shapes carbon/amorphous carbon nano-complex, The nano-complex microstructure is Co3In C@onion shape carbon nuclear shell structure nanos capsule insertion amorphous carbon nanometer sheet.Wherein Co3The particle diameter of C@onion shape carbon Nano capsules is 2~15nm, and kernel is Co3C nano particle, shell is onion shape carbon.
Embodiment 5
Lid 1 on device shown in Fig. 1 is opened, making negative electrode 2 with graphite is fixed on chuck 8, institute consumable anode target 4 Composition is pure cobalt powder and coal dust (mass ratio 45:55) block being pressed into, is placed on the copper anode 7 of logical cooling water, in logical cooling water Copper anode and target between be graphite crucible 9.Kept between negative electrode graphite electrode and 4 anode target materials cobalt-coal powdered block The distance of 10mm.Lid 1 on lid mounted device, leads to cooling water a, whole operating room is vacuumized by valve 3 after, is passed through argon gas b and hydrogen Gas c, the partial pressure of argon gas is 0.01MPa, and the partial pressure of hydrogen is 0.01MPa, connects DC pulse power supply 10, and voltage is 40V.Arc light Adjustment work electric current keeps relative stability with voltage in discharge process.Co is obtained3C@onions shapes carbon/amorphous carbon is nano combined Thing, the nano-complex microstructure is Co3In C@onion shape carbon nuclear shell structure nanos capsule insertion amorphous carbon nanometer sheet.Its Middle Co3The particle diameter of C@onion shape carbon Nano capsules is 2~15nm, and kernel is Co3C nano particle, shell is onion shape carbon.

Claims (3)

1. a kind of Co3C@onions shapes carbon/amorphous carbon nano-complex, it is characterised in that the nano-complex microstructure is Co3C@onion shape carbon nuclear shell structure nanos capsule is embedded in amorphous carbon nanometer sheet；Wherein, Co3The grain of C@onion shape carbon Nano capsules Footpath is 2~15nm, and kernel is Co3C nano particle, shell is onion shape carbon.
2. Co as claimed in claim 13The preparation method of C@onions shapes carbon/amorphous carbon nano-complex, it is characterised in that：Should Material is that original position prepares under working gas using plasma arc discharge technology；Wherein：
It is negative electrode to use graphite electrode, and cobalt-coal powdered block is anode target material, negative electrode graphite electrode and anode target material cobalt-coal dust The distance of 2~30mm is kept between last block；The voltage of arc discharge is 10~40V；Working gas is argon gas and hydrogen gas； Mass percent in the anode material shared by cobalt is 30~50%；The partial pressure of the argon gas is 0.01~0.5MPa, hydrogen The partial pressure of gas is 0.01~0.3MPa.
3. the Co that such as claim 2 preparation method is obtained3C@onions shapes carbon/amorphous carbon nano-complex is used as lithium ion battery The application of negative material.
CN201710017966.XA 2017-01-11 2017-01-11 Co3C@onion-shaped carbon/amorphous carbon nano-composite as well as preparation method and application thereof Pending CN106711422A (en)

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