CN103855361A - Method for preparing nitrogen-doped porous carbon nanofiber cloth - Google Patents

Method for preparing nitrogen-doped porous carbon nanofiber cloth Download PDF

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CN103855361A
CN103855361A CN201410122929.1A CN201410122929A CN103855361A CN 103855361 A CN103855361 A CN 103855361A CN 201410122929 A CN201410122929 A CN 201410122929A CN 103855361 A CN103855361 A CN 103855361A
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porous carbon
carbon nanofiber
nitrogen
activation
nanofiber cloth
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CN103855361B (en
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康飞宇
楠顶
黄正宏
沈万慈
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Tsinghua University
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/022—Electrodes made of one single microscopic fiber
    • 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

Abstract

The invention relates to a method for preparing nitrogen-doped porous carbon nanofiber cloth. The nitrogen-doped porous carbon nanofiber cloth is prepared by adding a nitrogen-rich compound into an organic solution, electrospinning and subsequent carbonizing-activating, has a self-support structure, omits preparation steps of size mixing, coating and the like, needs no conductive agent or binder, and can be directly used as the negative electrode of a lithium ion battery. The electrochemical performance of the negative electrode material of the lithium ion battery is improved by doping nitrogen and activating and forming pores; compared with a commercial graphite lithium ion battery negative electrode material, the nitrogen doping porous carbon nanofiber cloth used as the negative electrode material of the lithium ion battery has simple steps for preparing the electrode, has higher specific capacity, good power performance and circulatory stability. The method also can be used as the electrode material of super capacitors and other novel batteries.

Description

The preparation method of nitrating porous carbon nanofiber cloth
Technical field
The present invention relates to material with carbon element and technical field of chemical power, particularly a kind of preparation method of the nitrating porous carbon nanofiber cloth as lithium ion battery negative material.
Background technology
Energy shortage and environmental pollution are two hang-ups that world today's human society must be faced.Solve this two hang-up, scholars' approach of generally believing has two: one, finds and develops new clean energy resource and substitute existing fossil energy; The 2nd, improve existing secondary cell performance.
Other traditional secondary battery technology of comparing, the advantages such as operating voltage is high, volume is little, quality is light, specific energy is high because having for lithium ion battery, memory-less effect, self discharge are little, have extended cycle life, environmental pollution is little, can charge safely and fast, operating temperature range is wide are widely used in mobile with fields such as electronic equipment (as mobile phone, notebook computer, video camera, digital camera etc.), electric automobile energy technology, extensive energy-storage pile, ups power, space technology, Medical Instruments and national defense and military, are called as and have the secondary cell technology that uses future most.Since entering the new century, the new-energy automobile fast developments such as hybrid vehicle/pure electric automobile, make the research and development of power-type lithium ion battery start new climax, how to improve energy density, power density, useful life and the fail safe of lithium ion battery, and reduce costs, be the hot subject of current research, its key is that high performance electrode material comprises the research and development of high-performance negative material.Graphite is the commercial li-ion cell negative electrode material of current main-stream.But because of its capacity low (theoretical specific capacity is 372mAh/g), power-performance is poor etc., and reason is difficult to meet electrokinetic cell anticathode material high power capacity, high power density and long-life requirement.
In order to continue to improve the performance of lithium ion battery, each state is all at the better Novel anode material of research and development performance.Along with the development of nanometer technology and modification technology, the fibrous carbon material that some are novel and porous carbon materials show good lithium ion battery negative material performance.But current reported fibrous carbon material or porous carbon materials be because chemical property is poor, high cost, preparation section is numerous and diverse, can not stablize the reasons such as controlled acquisition high-performance negative material is difficult to meet current demand.
Electrospun (Electrospinning), claims again electrostatic spinning, is the important method of preparing monodimension nanometer material, almost any solvable or fusible Polymer materialspreparation can be become to continuous fiber, and fibre diameter can reach nanoscale.Electric spinning device mainly comprises the collecting board of high-voltage DC power supply, conduction and the solution weight feed equipment with syringe needle.The positive pole of high voltage source is connected with syringe needle, and negative pole is connected with collecting board, and spinning voltage is generally at 20-35kV.Syringe needle can vertically be placed with collecting board, also can horizontal positioned, and laboratory is used its distance to be generally 10-30cm.When use, precursor solution is sent from syringe needle with certain speed, now precursor solution positively charged.Under the effect of electric field force, charged liquid forms Taylor cone (Taylor coin) at syringe needle, and sprays to negative pole collecting board from conehead with fibers form.Under the effect of electrostatic field, fiber is splitting gradually, and solvent volatilizees gradually, and fibre diameter reduces, and finally on collecting board, obtains nanofiber.Generally, the end product of Electrospun is the film being formed by the random braiding of precursor fibre, and structure is similar to nonwoven fabrics.
Summary of the invention
In order to overcome the shortcoming and defect of prior art, the object of the present invention is to provide a kind of preparation method of nitrating porous carbon nanofiber cloth, adopt raw material with low cost, use the method for Electrospun and follow-up carbonization-activation to prepare nitrating porous carbon nanofiber cloth, simple to operate, aperture is controlled and be evenly distributed; The material of preparing gained has the features such as high conductivity, high-specific surface area, abundant hole, is conducive to improve material specific capacity, increases electrode/electrolyte contact area, shortens lithium ion transmission range, improves negative material power-performance.
In order to achieve the above object, the present invention is achieved through the following technical solutions:
Step 1, polymer and nitrogen-enriched compounds are dissolved in solvent, form uniform polymer solution; Liquid quality fraction is 5%～20%, and polymer and nitrogen-enriched compounds mass ratio are 1 ︰ (1～9);
Described polymer is a kind of in polyacrylonitrile (PAN), polyimides (PI), phenolic resins (Resol) or pitch;
Described nitrogen-enriched compounds is a kind of in melamine (Mel), urea, gelatin (Gelatin), polyaniline or polypyrrole;
Described solvent is a kind of in DMF (DMF), DMA (DMAc), 1-METHYLPYRROLIDONE (NMP) or oxolane (THF) solution;
Step 2, using polymer solution as precursor solution for Electrospun, obtain diameter and be tens nanometers to the fiber of several microns, the mutual random mat of fiber forms non-woven fibre cloth; Polymer solution is under the effect of high-voltage DC power supply, can overcome surface tension, form and spray thread, in course of injection, solvent constantly volatilizees, the unsteadiness of jet and the effect of electrostatic force are constantly stretched jet, and jet splitting phenomenon occurs sometimes, finally on gatherer, obtain the non-woven fibre cloth being made up of to the fiber of several microns for tens nanometers diameter;
Described Electrospun design parameter is: by presoma with 0.5～2.0mL h -1constant rate of speed be pumped to each nozzle of electric spinning device with micro quantitative determination, Electrospun is with tack stainless steel syringe needle as nozzle, internal diameter is about 1mm; Collecting board is conductor, as graphite paper, metallic plate; Syringe needle and graphite cake spacing are 10～20cm, and voltage is 15～25kV;
Step 3, Electrospun preliminary treatment at 80～350 ℃ that step 2 is obtained, heating 2～10h; After preliminary treatment, Electrospun is under nitrogen protection, and high temperature cabonization and activation 1～3h, obtain nitrating porous carbon nanofiber cloth;
Described carbonization and activation heating rate are 5～10 ℃ of min -1, carbonization and activation temperature are 600～1200 ℃, and carbonization protective atmosphere is nitrogen, and activation adopts steam activation or two kinds of activation methods of ammonia activation;
Step 4, the nitrating porous carbon nanofiber cloth that step 3 is obtained are directly used as lithium ion battery negative.
The present invention has following advantage and effect with respect to prior art:
(1) cost of material that the present invention selects is cheap.Institute's distribution spinning precursor solution good spinnability, has good technology stability.
(2) the present invention adopts the method for Electrospun and follow-up carbonization-activation to prepare nitrating porous carbon nanofiber cloth, simple to operate, and aperture is controlled and be evenly distributed.This material has the features such as high conductivity, high-specific surface area, abundant hole, is conducive to improve material specific capacity, increases electrode/electrolyte contact area, shortens lithium ion transmission range, improves negative material power-performance.
(3) gained of the present invention has self supporting structure nitrating porous carbon nanofiber cloth, and as lithium ion battery negative, preparation section is simple, and chemical property is good, has good specific capacity, power-performance and cyclical stability.
(4) technique of the present invention is simple, prepares electrode operation without size mixing, film etc., without adding the additives such as any conductive agent and binding agent, not harsh to operation and environmental requirement, for technology is provided by the simple and easy to do condition that provides.
In addition also there is other application in the present invention.As:
(1) electrode material for super capacitor.Nitrating porous carbon nanofiber cloth is suitable as electrode material for super capacitor very much, because it has larger specific area and good pore structure, and has higher conductivity through nitrating.
(2) lithium sulfur battery anode material.The porosity characteristic of nitrating porous carbon nanofiber cloth and higher conductivity are suitable as the carrier of element sulphur as lithium sulfur battery anode material very much.
(3) the empty cell positive material of lithium.The porosity characteristic of nitrating porous carbon nanofiber cloth and higher conductivity are suitable as the carrier of catalyst as the empty cell positive material of lithium very much.
(4) anode material of lithium-ion battery.The porosity characteristic of nitrating porous carbon nanofiber cloth and higher conductivity are suitable as anode material of lithium-ion battery very much.
Accompanying drawing explanation
Fig. 1 is that nitrating porous carbon nanofiber cloth prepared by example 2 of the present invention is used as lithium ion battery negative material at 25 ℃, 50mA g -1charge/discharge capacity, coulomb efficiency and cyclical stability figure under current density.
Fig. 2 is the stereoscan photograph of the nitrating porous carbon nanofiber cloth prepared of example 2 of the present invention.
Embodiment
Below in conjunction with example, the present invention is described further, but embodiments of the present invention are not limited to this.
Embodiment mono-
(1) selecting melamine is nitrogen-enriched compounds, and PAN is polymer, preparation precursor solution.First prepare 10%PAN solution, and add Mel:PAN=1:2(mass ratio) melamine (Mel), 70 ℃ of water bath with thermostatic control mechanical agitation 10h.
(2) by precursor solution with 1.0mL h -1constant rate of speed be pumped to electric spinning device with micro quantitative determination, Electrospun is with tack stainless steel syringe needle as nozzle, internal diameter is about 1mm, collecting board is graphite paper, syringe needle and graphite cake spacing are 20cm, voltage is 25kV.
(3) pre-oxidation: gained electricity spinning fibre cloth, 5 ℃ of min -1be raised to 250 ℃ of insulation 1h from room temperature, then at 2 ℃ of min -1, rise to 260 ℃ and 270 ℃, be incubated respectively 1h and 2h and reach the object of pre-oxidation.
Carbonization and activation: under nitrogen protection, by pre-oxidation electricity spinning fibre cloth, 5 ℃ of min -1be raised to 850 ℃ from room temperature, 850 ℃ of insulation 30min, and logical 20% concentration (volume ratio) water vapour 30min, obtain nitrating porous carbon nanofiber cloth.
(4) the nitrating porous carbon nanofiber cloth obtaining, directly as electrode, is assembled into 2032 button cell test chemical properties in the situation that not adding any conductive agent and binding agent.Electrolyte is the mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC), EC:DMC=1:1(volume ratio), lithium salts is 1M LiPF 6.Test condition is constant current charge-discharge, voltage range 0～3.0V.
The nitrating porous carbon nanofiber cloth ion cathode material lithium that the method obtains has higher specific capacity and good high rate performance.At 50mA g -1under current density, first charge-discharge specific capacity is respectively 1233mAh g -1with 1569.8mAh g -1, coulomb efficiency is 78.5% first.Through 50 circulations, charging capacity is 513mAh g -1.
Embodiment bis-
In use-case 1, identical method is prepared nitrating porous carbon nanofiber cloth, and difference is to use ammonia activation.
With reference to Fig. 1, the prepared nitrating porous carbon nanofiber cloth of the present embodiment is used as lithium ion battery negative material at 25 ℃, 50mA g -1charge/discharge capacity, coulomb efficiency and cyclical stability figure under current density.
The nitrating porous carbon nanofiber cloth ion cathode material lithium that the method obtains has higher specific capacity, good high rate performance and stable circulation performance.At 50mA g -1under current density, first charge-discharge specific capacity is respectively 1323mAh g -1with 2245mAh g -w, coulomb efficiency is 59% first.Through 50 circulations, charging capacity is 1150mAh g -1.
Fig. 2 is the stereoscan photograph of the nitrating porous carbon nanofiber cloth prepared of the present embodiment.As can be seen from the figure, even aperture distribution.
Embodiment tri-
In use-case 1, identical method is prepared nitrating porous carbon nanofiber cloth, and difference is with urea as nitrogen-enriched compounds.
The nitrating porous carbon nanofiber cloth ion cathode material lithium that the method obtains is at 50mA g -1under current density, first charge-discharge specific capacity is respectively 750mAh g -1with 1445mAh g -1, coulomb efficiency is 52% first.Through 50 circulations, charging capacity is 550mAh g -1.
Embodiment tetra-
In use-case 2, identical method is prepared nitrating porous carbon nanofiber cloth, and difference is with urea as nitrogen-enriched compounds.
The nitrating porous carbon nanofiber cloth ion cathode material lithium that the method obtains is at 50mA g -1under current density, first charge-discharge specific capacity is respectively 876mAh g -1with 1552mAh g -1, coulomb efficiency is 56% first.Through 50 circulations, charging capacity is 676mAh g -1.
Embodiment five
In use-case 2, identical method is prepared nitrating porous carbon nanofiber cloth, and difference is that polymer selects polyimides, and solvent is selected DMA (DMAc).
The nitrating porous carbon nanofiber cloth ion cathode material lithium that the method obtains is at 50mA g -1under current density, first charge-discharge specific capacity is respectively 920mAh g -1with 1723mAh g -1, coulomb efficiency is 53% first.Through 50 circulations, charging capacity is 760mAh g -1.
The explanation of above example is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that and do not departing under the prerequisite of this method Spirit Essence and principle, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of the claims in the present invention.

Claims (3)

1. the preparation method of nitrating porous carbon nanofiber cloth, is characterized in that, comprise the following steps,
Step 1, polymer and nitrogen-enriched compounds are dissolved in solvent, form uniform polymer solution; Liquid quality fraction is 5%～20%, and polymer and nitrogen-enriched compounds mass ratio are 1 ︰ (1～9);
Described polymer is the one in polyacrylonitrile (PAN), polyimides (PI), phenolic resins (Resol) or pitch;
Described nitrogen-enriched compounds is the one in melamine (Mel), urea, gelatin (Gelatin), polyaniline or polypyrrole;
Described solvent is the one in DMF (DMF), DMA (DMAc), 1-METHYLPYRROLIDONE (NMP) or oxolane (THF) solution;
Step 2, using polymer solution as precursor solution for Electrospun, obtain diameter and be tens nanometers to the fiber of several microns, the mutual random mat of fiber forms non-woven fibre cloth; Polymer solution is under the effect of high-voltage DC power supply, can overcome surface tension, form and spray thread, in course of injection, solvent constantly volatilizees, the unsteadiness of jet and the effect of electrostatic force are constantly stretched jet, and jet splitting phenomenon occurs sometimes, finally on gatherer, obtain the non-woven fibre cloth being made up of to the fiber of several microns for tens nanometers diameter;
Step 3, Electrospun preliminary treatment at 80～350 ℃ that step 2 is obtained, heating 2～10h; After preliminary treatment, Electrospun is under nitrogen protection, and high temperature cabonization and activation 1～3h, obtain nitrating porous carbon nanofiber cloth;
Step 4, the nitrating porous carbon nanofiber cloth that step 3 is obtained are directly used as lithium ion battery negative.
2. the preparation method of nitrating porous carbon nanofiber cloth according to claim 1, is characterized in that,
Described Electrospun design parameter is: by presoma with 0.5～2.0mL h -1constant rate of speed be pumped to each nozzle of electric spinning device with micro quantitative determination, Electrospun is with tack stainless steel syringe needle as nozzle, internal diameter is about 1mm.Collecting board is conductor, as graphite paper, metallic plate.Syringe needle and graphite cake spacing are 10～20cm, and voltage is 15～25kV.
3. the preparation method of nitrating porous carbon nanofiber cloth according to claim 1, is characterized in that, described carbonization and activation heating rate are 5～10 ℃ of min -1, carbonization and activation temperature are 600～1200 ℃, and carbonization protective atmosphere is nitrogen, and activation adopts steam activation or two kinds of activation methods of ammonia activation.
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