CN103088465A - Hollow graphite carbon nanometer sphere in-situ modification amorphous carbon nanometer fibers or carbon nano-tubes and preparation method thereof - Google Patents
Hollow graphite carbon nanometer sphere in-situ modification amorphous carbon nanometer fibers or carbon nano-tubes and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to hollow graphite carbon nanometer sphere in-situ modification amorphous carbon nanometer fibers/carbon nano-tubes and a preparation method thereof. The preparation method comprises the following steps: preparing a spinning solution; preparing and drying a composite nanometer fiber precursor; carrying out carbonization on the composite nanometer fiber precursor to obtain composite nanometer fibers or nano-tubes; and carrying out an acid treatment on the composite nanometer fibers or the nano-tubes, and drying to obtain the hollow graphite carbon nanometer sphere in-situ modification amorphous carbon nanometer fibers/carbon nano-tubes. With the present invention, the carbon nanometer fibers/carbon nano-tubes can be further utilized to prepare an electrode and assemble a lithium ion battery or a supercapacitor. According to the preparation method, the disadvantage of high temperature graphitization required by macromolecule cyclization is overcome, a specific surface area, a conductivity, and capacity for resisting structure destruction due to volume expansion caused by external causes of the composite nanometer fibers/nano-tubes are improved, and the assembled lithium ion battery and the supercapacitor device have characteristics of high capacity, good rate, high stability and the like.
Description
Technical field
The present invention relates to a kind of carbon nanomaterial, more particularly, relate to a kind of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or CNT and preparation method thereof.
Background technology
Along with the progress of society, economic development increases day by day to the demand of non-renewable energy resources, will inevitably cause the aggravation of the exhaustion of the non-renewable resources such as oil, coal, natural gas and environmental pollution, greenhouse effects.For this reason, the utilization of new forms of energy, the exploitation that economizes energy technology, Environmental Technology and the comprehensive high-efficiency middle heavy problem that become to attach most importance to.The electric equipment products such as Development of EV, mobile phone, notebook are imperative.Ultracapacitor and lithium ion battery have obvious advantage in these fields, and they can satisfy the requirements such as high power, high life, high stability.The carbon current material due to low price, nontoxic, stablize high and be subject to social favor.Such as the main materials such as present commercial lithium ion battery and ultracapacitor are exactly that material with carbon element forms.But the development of high power capacity due to the material with carbon element structural constraint, therefore improve the material with carbon element capacity extremely urgent.
The nanometer of material has given material higher performance, even new function.Carbon nanomaterial is owing to having high-specific surface area, and the ability of absorption electrolyte intermediate ion improves, thereby has improved the capacity of material with carbon element.At present, a series of synthetic technologys have successfully been prepared various carbon nanomaterials, for example: chemical method, calcining technology, collosol and gel etc.The setting of parameter determines structure and the performance thereof of end product.Therefore, controlling the ability with high performance product is final purpose for any one preparation method.Relative these methods, electrostatic spinning technique is under action of high voltage, electric field force overcomes the surface tension of solution, hemispherical drop becomes taper (Taylor cone), and then then the surface tension that charged jet can overcome solution forms fiber web on unordered arrival receiving device from " taper (Taylor cone) " ejaculation.Compare with other method, but the simple continuous production of electrostatic spinning process, expense is not high and the characteristics such as efficient, the more important thing is that its in-situ modification ability is high, but industrialization, be considered to prepare the best approach of nano material, the nanofiber of preparation/its diameter of pipe 10nm～10 μ m.Electrostatic spinning technique of the present invention below Here it is.
Carbon nano-fiber/CNT has the design feature of nano material, with traditional material with carbon element (graininess) relatively, have that specific area is large, the chemism high.Although carbon nano-fiber/CNT can improve the capacity of ultracapacitor and lithium ion battery, how further to improve capacity and stability is still restricting carbon nano-fiber/carbon nanotubes application.Such as: when carbon nano-fiber/CNT was applied in lithium ion battery, its stability was low, capacity loss is fast because the volumetric expansion that does not have to bring in unnecessary spatial stability charge and discharge process causes; Need very large specific area to remove to store electrolyte ion to improve its capacity when in addition, carbon nano-fiber/nanotube is as ultracapacitor.Therefore prepare a kind of novelty, high power capacity, high stability, carbon nano-fiber/CNT of high life be the difficult problem that numerous researchers go all out to capture.
Summary of the invention
The technical problem to be solved in the present invention is, space for existing carbon nano-fiber/CNT causes the defective that stability is low, capacity loss is fast not, a kind of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber/CNT and preparation method thereof is provided, the lithium ion battery that the hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber/CNT for preparing with the method is assembled into or electrode of super capacitor have the advantages such as energy density is high, good stability, life-span length, can be applicable to the fields such as lithium ion battery and ultracapacitor.
For realizing that purpose of the present invention adopts technical scheme as follows: the invention provides the preparation method of a kind of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or CNT, sequentially comprise the steps:
(1) preparation electrostatic spinning liquid: but be mixed with uniform electrostatic spinning liquid with polar solvent with after transition metal salt and cyclisation macromolecule resin mix and blend, but wherein but the macromolecule resin of cyclisation described in electrostatic spinning liquid accounts for 5～50% of described cyclisation macromolecule resin and polar solvent quality sum; But described transition metal salt accounts for 0.5～50% of described cyclisation macromolecule resin and polar solvent quality sum;
(2) preparation of composite nano fiber precursor: with the electrostatic spinning liquid of step (1) preparation by electrospinning device under the high-pressure electrostatic effect, be prepared into the composite nano fiber precursor;
(3) drying: described composite nano fiber precursor is dry in a vacuum;
(4) calcining: the carbonization in inert atmosphere of dried composite nano fiber precursor is become composite nano fiber or nanotube;
(5) acid treatment and dry: the composite nano fiber after carbonization or nanotube are processed with acid, and drying makes described hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or CNT in a vacuum.
In the preparation method according to hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber of the present invention or CNT, described step (1) but in the described cyclisation macromolecule resin that adopts comprise: one or more combinations in Kynoar, polyvinyl alcohol, pitch, polypyrrole, polyvinylpyridine alkane ketone, poly(ethylene oxide), polymethyl methacrylate, PLA, polyacrylonitrile and polystyrene.
In the preparation method according to hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber of the present invention or CNT, the transition metal salt that adopts in described step (1) comprises: one or more combinations in Schweinfurt green, copper chloride, copper sulphate, copper carbonate, nickel acetate, nickel chloride, nickelous carbonate, nickelous sulfate, ferric acetate and iron chloride.
In the preparation method according to hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber of the present invention or CNT, the polar solvent that adopts in described step (1) is one or more combinations in water, ethanol, dimethyl formamide, oxolane, acetone and dimethyl sulfoxide (DMSO).
In the preparation method according to hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber of the present invention or CNT, in described step (2), the electrospinning parameter is: voltage 9～25kV, collection distance are that 5～20cm, feeding speed are 0.01～1mL/h; Wherein the nozzle of electrospinning device is single shaft, coaxial or three coaxial.
In the preparation method according to hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber of the present invention or CNT, described in described step (3), the dry environment of composite nano fiber precursor is: vacuum is dry 1～24h under 40～90 ℃ of 0.04～0.01MPa, temperature; Described in described step (5), composite nano fiber or nanotube at the dry environment after acid treatment are: vacuum is dry 1～48h under 40～200 ℃ of 0.04～0.005MPa, temperature.
In the preparation method according to hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber of the present invention or CNT, in described step (4), dried composite nano fiber precursor is calcined 1～20h and formed composite nano fiber or the nanotube of carbonization in calcining heat under inert atmosphere protection under 400～1000 ℃; Wherein said inert gas can be nitrogen, argon gas, hydrogen/argon gas composite gas, hydrogen/nitrogen composite gas.
In the preparation method according to hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber of the present invention or CNT, nanofiber or nanotube acidic treatment at 20～80 ℃ of temperature of carbonization after calcining in described step (5), one or more combinations in nitric acid, sulfuric acid, hydrofluoric acid and hydrochloric acid are adopted in wherein said acid.
Hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or CNT that the present invention also provides a kind of preparation method as above to make, its pattern is a kind of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or a kind of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanotube, the diameter of wherein said hollow plumbago carbon nanometer bead 2～100nm and wherein the thickness of graphitic carbon at 1～100nm; The diameter of described carbon nano-fiber is at 50～2000nm, and perhaps the diameter of described CNT is at 50～2500nm, and the pipe diameter of CNT is at 30～600nm.
The present invention also provides a kind of electrode, and described electrode is assembled by following material: the hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or the CNT that make according to preparation method as above.
The present invention also provides a kind of lithium ion battery or ultracapacitor, has according to electrode as above, and the reversible capacity of wherein said lithium ion battery is 400～1100mAhg
-1The reversible capacity of described ultracapacitor is 70～200F/g.
Implement hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber of the present invention or CNT and preparation method thereof, have following beneficial effect:
(1) the hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber of the present invention's preparation/carbon nano tube structure is novel, specific area is large, the space is many, conductance is high, the ability to structural deterioration that the opposing outside cause causes volumetric expansion to bring is good, easily reclaim, can be recycled, it is high that the lithium ion battery that the hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber/CNT for preparing with the method is assembled into or electrode of super capacitor have energy density, good stability, the advantages such as the life-span is long, can be applicable to the fields such as lithium ion battery and ultracapacitor,
(2) the present invention adopts electrostatic spinning technique to prepare hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber/CNT, and equipment is simple, and processing ease can prepare in a large number.
The specific embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, the present invention is further elaborated.
In the carbon nanomaterial of the inventive method preparation according to the difference of preparation condition, its surface topography can become hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanotube, (wherein the thickness of graphitic carbon forms at the CNT of 50～2500nm at carbon nano-fiber or the diameter of 50～2000nm with diameter 1～100nm), and wherein the caliber of CNT is at 30～600nm at the hollow plumbago carbon nanometer bead of 2～100nm by diameter.
The preparation method of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber/CNT provided by the invention sequentially comprises the steps:
(1) preparation electrostatic spinning liquid: but but be mixed with uniform electrostatic spinning liquid with the polar solvent that can be under stirring condition transition metal salt and cyclisation macromolecule resin be stirred into uniform state with after transition metal salt and cyclisation macromolecule resin mix and blend, but wherein the percentage by weight of the cyclisation macromolecule resin in electrostatic spinning liquid and transition metal salt is as follows: but but the cyclisation macromolecule resin accounts for 5～50% of cyclisation macromolecule resin and polar solvent quality sum; But transition metal salt accounts for 1～50% of cyclisation high-molecular resin solution quality.But wherein but the cyclisation high-molecular resin solution refers to be comprised of cyclisation macromolecule resin and polar solvent.Therefore, but but above-mentioned cyclisation macromolecule resin percentage by weight refers to the cyclisation macromolecule resin accounts for the percentage that can spin macromolecule resin and polar solvent sum.But the percentage of transition metal salt refers to transition metal salt and accounts for the percentage of cyclisation high-molecular resin solution.But cyclisation macromolecule resin of the present invention refers to macromolecule resin under inert gas shielding, and in the process of high-temperature calcination, macromolecular chain can be cyclized into the interchangeableization macromolecule resin of graphitized carbon material.
(2) preparation of composite nano fiber precursor: the electrostatic spinning liquid in step (1) under the high-pressure electrostatic effect, is prepared the composite nano fiber precursor by electrospinning device;
(3) drying: the composite nano fiber precursor is dry in a vacuum;
(4) calcining: the carbonization under inert atmosphere protection, hot conditions of dried composite nano fiber precursor is formed composite nano fiber or nanotube, i.e. transition metal/carbon nano-fiber or nanotube;
(5) acid treatment and dry: the composite nano fiber or the nanotube that obtain are used acid treatment at a certain temperature; Composite nano fiber or the nanotube drying of acid treatment are made described hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or CNT.
When needs are prepared into electrode with this carbon nanomaterial, again by step (6): carbon nano-fiber or the CNT of preparation electrode after with dried acid treatment is assembled into electrode.And can further take this electrode as the basis, be assembled into lithium ion battery provided by the invention or ultracapacitor.
In above-mentioned preparation process; wherein step (1) but in the cyclisation macromolecule resin refer under inert gas shielding; but can be in the high temperature cabonization process cyclisation and produce the macromolecule resin of material with carbon element, such as one or more combinations of Kynoar, polyvinyl alcohol, pitch, polypyrrole, polyvinylpyridine alkane ketone, poly(ethylene oxide), polymethyl methacrylate, PLA, polyacrylonitrile, polystyrene etc.Transition metal salt refers under inert gas shielding; form transition metal at the high-temperature calcination late transition metal salt; and but the carbonization of catalysis cyclisation macromolecule resin becomes graphited carbon in this process, such as one or more combinations of Schweinfurt green, copper chloride, copper sulphate, copper carbonate, nickel acetate, nickel chloride, nickelous carbonate, nickelous sulfate, ferric acetate, iron chloride etc.Described polar solvent refers to but transition metal salt and cyclisation macromolecule resin being stirred into uniform polar solvent by stirring, and the present invention chooses one or more combinations of water, ethanol and dimethyl formamide, oxolane, acetone and dimethyl sulfoxide (DMSO).The macromolecule that certainly other can cyclisation, can rise catalysis transition metal salt, but to dissolve simultaneously transition metal salt also available with the solvent of the material of cyclisation macromolecule resin, this is that those skilled in the art test and can find by limited number of time.But thereby can say macromolecule resin that all can cyclisation, can rise catalytic action transition metal salt, can dissolve the solvent of transition metal salt and the material of cyclisation macromolecule resin, be applied to preparation method of the present invention and all belong to protection scope of the present invention.
Wherein in step (2), the composite nano fiber precursor is by Electrospun equipment, in the electrospinning parameter is: voltage 9～25kV, collection distance are that 5～20cm, feeding speed are 0.01～1mL/h.Wherein the nozzle of electrospinning device can be single shaft, coaxial and be three coaxial.When wherein preparing hollow plumbago carbon in-situ modification amorphous carbon nanofiber with the single shaft nozzle, but spinning solution is the mixed solution of cyclisation macromolecule resin and transition metal salt; When preparing hollow plumbago carbon in-situ modification amorphous carbon nanotube with coaxial nozzle, the spinning solution of interior axle is mineral oil or vegetable oil, but the spinning solution of outer shaft is the mixed solution of cyclisation macromolecule resin and transition metal salt.In when preparing hollow plumbago carbon modification amorphous carbon nanotube with three axles, axle is mineral oil or vegetable oil, but jackshaft is the mixed solution of cyclisation macromolecule resin and transition metal salt, but outer shaft is the cyclisation high-molecular resin solution; Perhaps but jackshaft is the cyclisation high-molecular resin solution, but outer shaft is the mixed solution of cyclisation macromolecule resin and transition metal salt.It is also passable that certain other combinations finally can be prepared hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber/CNT.
Wherein the composite nano fiber precursor is to be dry 1～24h under 40～90 ℃ of 0.04～0.01MPa, temperature in vacuum in step (3).Nanofiber/the nanotube of the carbonization in step (5) after acid treatment is to be dry 1～48h under 40～200 ℃ of 0.04～0.005MPa, temperature in vacuum.
Wherein in step (4), dried composite nano fiber precursor is calcined 1～20h in calcining heat under inert atmosphere protection under 400～1000 ℃ and form carbonization composite nano fiber/nanotube.Wherein inert gas can be nitrogen, argon gas, hydrogen/argon gas composite gas, hydrogen/nitrogen composite gas.Composite nano fiber/nanotube after carbonization after calcining in addition is acidic treatment at 20～80 ℃ of temperature, if the acid that wherein transition metal can be dissolved out can, such as one or more combinations of nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid.
The electrode of the present invention's preparation can be the electrode of lithium ion battery, can be also the electrode of ultracapacitor.Wherein its reversible capacity of lithium ion cell electrode is 400～1100mAhg
-1, the reversible capacity of ultracapacitor is 70～200g/F.
In sum, it is raw material that the present invention adopts transition metal salt, but utilizes electrostatic spinning technique that it is evenly distributed in the macromolecule resin of cyclisation, with the carbonization under inert atmosphere of electrospinning composite fibre.At this moment transition metal salt resolves into transition metal nanoparticles, under its catalytic action, the carbon of transiting metal surface becomes graphited carbon with carbonization, then after acid treatment, forms the amorphous carbon nano-fiber/CNT of a kind of hollow plumbago carbon nanometer bead in-situ modification.Amorphous carbon nano-fiber/CNT of original position generation hollow plumbago carbon nanometer bead modification that this invention proposes and preparation method thereof has overcome the cyclisation macromolecule needs the graphited shortcoming of high-temperature, realized the amorphous carbon nano-fiber/CNT of hollow plumbago carbon nanometer bead in-situ modification, improved simultaneously the specific area of composite nano fiber/nanotube, electrical conductivity, and resist the ability to structural deterioration that outside cause causes volumetric expansion to bring.The electrode of being made by the amorphous carbon nano-fiber/carbon nano-tube material of hollow plumbago carbon nanometer bead in-situ modification, be assembled into lithium ion battery and ultracapacitor device, present that capacity is high, multiplying power good, stable high, have important application prospect in fields such as high performance lithium ion battery and ultracapacitors.
The present invention is described according to specific embodiment, but it will be understood by those skilled in the art that when not breaking away from the scope of the invention, can carry out various variations and be equal to replacement.In addition, for adapting to specific occasion or the material of the technology of the present invention, can carry out many modifications and not break away from its protection domain the present invention.Therefore, the present invention is not limited to specific embodiment disclosed herein, and comprises that all drop into the embodiment of claim protection domain.
Example one
1, preparation electrostatic spinning solution: with 7.5g polyvinyl alcohol (PVA), 4g nickel chloride (NiCl
2) and the mixing of 67.5mL distilled water, the spinning solution of formation homogeneous after stirring a period of time under 80 ℃.
2, by electrospinning device, at voltage 20kV, spinning head and the receiving device feed flow velocity 0.4mL/h apart from 18cm, spinning solution, the spinning solution electrospinning prepares PVA/NiCl
2The composite nano fiber precursor.
3, with the PVA/NiCl for preparing
2The composite nano fiber precursor is dry 8h in vacuum drying chamber (vacuum is 0.03MPa, temperature 70 C).
4, dried PVA/NiCl
2The composite nano fiber precursor is at H
2/ N
2The lower 500 ℃ of calcining 2h of inert atmosphere.Prepare diameter at the C/Ni of 50～100nm scope composite nano fiber.
5, the C/Ni composite nano fiber is to process 48h under 30 ℃ of nitric acid in temperature, then at the dry 24h of vacuum drying chamber (vacuum is 150 ℃ of 0.01MPa, temperature), finally obtain hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber, wherein the diameter of hollow plumbago carbon nanometer bead is at 5～20nm, and the wall thickness of graphitic carbon is at 2～5nm.
6, prepare according to a conventional method li-ion electrode: take the preparation material with carbon element as working electrode, the lithium sheet is to electrode, Celgard 2400 is barrier film, with 1mol/L LiPF
6In EC: DMC: EMC (1: 1: 1 volume ratio) is electrolyte, is prepared into button cell.The test voltage scope is 0～3V.When current density is 50mA/g when carrying out abundant electric performance test, be 550mAhg than electric capacity
-1
Example two
1, preparation electrostatic spinning solution: with 2.5g PVA, 1.5g nickel acetate (Ni (Ac)
2) and the mixing of 22.5mL distilled water, the spinning solution of formation homogeneous after stirring a period of time under 80 ℃.
2, by electrospinning device, prepare PVA/Ni (Ac) at voltage 17kV, spinning head and receiving device apart from feed flow velocity 0.5mL/h, the above-mentioned spinning solution of tele-release of 18cm, spinning solution
2The composite nano fiber precursor.
3, with the PVA/Ni (Ac) for preparing
2The composite nano fiber precursor is dry 8h in vacuum drying chamber (vacuum is 0.02MPa, temperature 70 C).
4, dried PVA/Ni (Ac)
2The composite nano fiber precursor is at N
2The lower 500 ℃ of calcining 2h of inert atmosphere.Prepare diameter at the C/Ni of 50～200nm scope composite nano fiber.
5, the C/Ni composite nano fiber is to process 48h under 25 ℃ of hydrochloric acid in temperature, then at the dry 24h of vacuum drying chamber (vacuum is 120 ℃ of 0.01MPa, temperature), finally obtain hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber, wherein the diameter of hollow plumbago carbon nanometer bead is at 4～20nm, and the wall thickness of graphitic carbon is at 1～5nm.
6, prepare according to a conventional method ultracapacitor: take the preparation material with carbon element as working electrode, Pt is to electrode, with 1mol/L N
2SO
4Or KOH solution is electrolyte, is assembled into the capacitor unit of sandwich structure.The test voltage scope is 0～0.9V.When current density is 500mA/g when carrying out abundant electric performance test, be 80Fg than capacitance
-1
Example three
1, preparation electrostatic spinning solution: 1g polystyrene (PS), 0.5g Schweinfurt green (Cu (Ac)
2) and the mixing of 10mL dimethyl formamide, the spinning solution of formation homogeneous after stirring a period of time under 80 ℃.
2, by the electrospinning device of coaxial nozzle, be mineral oil (Oil), outer shaft PS/Cu (Ac) at interior axle
2Carry out spinning under mixed liquor, voltage 17kV, spinning head and the receiving device condition apart from the feed flow velocity 0.3mL/h of 20cm, interior outer shaft, preparation PS/Cu (Ac)
2The coaxial composite of@Oil.
3, with the PS/Cu (Ac) for preparing
2The coaxial composite precursor of@Oil is dry 4h in vacuum drying chamber (vacuum is 40 ℃ of 0.03MPa, temperature).
4, dried PS/Cu (Ac)
2The coaxial composite precursor of@Oil is at H
2/ N
2The lower 500 ℃ of calcining 2h of inert atmosphere.Prepare diameter at the C/Cu of 200～300nm scope composite nano tube, the diameter of pipe is 30～80nm.
5, the C/Cu composite nano tube is 40 ℃ in temperature, processes 48h under the mixed acid with nitric acid/sulfuric acid, then clean with distilled water, finally at the dry 24h of vacuum drying chamber (vacuum is 120 ℃ of 0.01MPa, temperature), finally obtain hollow plumbago carbon nanometer bead and modify the amorphous carbon nanotube, wherein the diameter of hollow plumbago carbon nanometer bead is at 4～20nm, and the wall thickness of graphitic carbon is at 1～4nm.
6, electrode assembling is pressed the described conventional method of embodiment 1 and is prepared and test, and when current density is 50mA/g when carrying out abundant electric performance test, is 560mAhg than electric capacity
-1
Example four
1, preparation electrostatic spinning solution: with 1g polyacrylonitrile (PAN), 1g nickel chloride (NiCl
2) and the mixing of 17mL dimethyl formamide, the spinning solution of formation homogeneous after stirring a period of time under 50 ℃.
2, by the electrospinning device of coaxial nozzle, be mineral oil (Oil), outer shaft PAN/NiCl at interior axle
2Carry out spinning under mixed liquor, voltage 16kV, spinning head and the receiving device condition apart from the feed flow velocity 0.2mL/h of 18cm, interior outer shaft, preparation PAN/NiCl
2The coaxial composite of@Oil.
3, with the PAN/NiCl for preparing
2@Oil composite nano fiber precursor is dry 4h in vacuum drying chamber (vacuum is 40 ℃ of 0.04MPa, temperature).
4, dried PAN/NiCl
2@Oil composite nano fiber precursor is at H
2/ Ar
2The lower 600 ℃ of calcining 3h of inert atmosphere.Prepare diameter at the C/Ni of 200～300nm scope composite nano tube, the diameter of pipe is 30～80nm.
5, the C/Ni composite nano tube is 25 ℃, use salt acid treatment 48h in temperature, then clean with distilled water, finally at the dry 48h of vacuum drying chamber (vacuum is 120 ℃ of 0.01MPa, temperature), finally obtain hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanotube, wherein the diameter of hollow plumbago carbon nanometer bead is at 5～30nm, and the wall thickness of graphitic carbon nano bead is at 2～6nm.
6, electrode assembling is pressed the described conventional method of embodiment 1 and is prepared and test, and when current density is 50mA/g when carrying out abundant electric performance test, is 546mAhg than electric capacity
-1
Example five
1, preparation electrostatic spinning solution: with 1g polyacrylonitrile (PAN), 1g nickel chloride (NiCl
2) and the mixing of 17mL dimethyl formamide, the spinning solution of formation homogeneous after stirring a period of time under 50 ℃.In addition, the polyvinylpyridine alkane ketone (PVP) with 1g is dissolved in the 30mL dimethyl formamide.
2, by the electrospinning device of three coaxial nozzles, be mineral oil (Oil), axis PAN/NiCl at interior axle
2Mixed liquor, outer shaft are to carry out spinning under PVP solution, voltage 17kV, spinning head and the receiving device condition apart from the feed flow velocity 0.01mL/h of 20cm, interior outer shaft, preparation PVP/PAN/NiCl
2@Oil composite.
3, with the PVP/PAN/NiCl for preparing
2@Oil composite nano fiber precursor is dry 4h in vacuum drying chamber (vacuum is 40 ℃ of 0.04MPa, temperature).
4, dried PVP/PAN/NiCl
2@Oil composite nano fiber precursor is at H
2/ Ar
2The lower 600 ℃ of calcining 2h of inert atmosphere.Prepare diameter at the C/Ni of 100～300nm scope composite nano tube, the diameter of pipe is 70nm.
5, the C/Ni composite nano tube is 30 ℃, processes 48h with nitration mixture (nitric acid and hydrochloric acid) in temperature, then clean with distilled water, finally at the dry 24h of vacuum drying chamber (vacuum is 130 ℃ of 0.01MPa, temperature), finally obtain hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanotube, wherein the diameter of hollow plumbago carbon nanometer bead is at 5～40nm, and the wall thickness of graphitic carbon nano bead is at 1～7nm.
6, electrode assembling is pressed the described conventional method of embodiment 1 and is prepared and test, and when current density is 50mA/g when carrying out abundant electric performance test, is 700mAhg than electric capacity
-1
Example six
1, preparation electrostatic spinning solution: with 4.5g pitch, 0.5g copper chloride (CuCl
2) and the mixing of 10g oxolane, the spinning solution of formation homogeneous after stirring a period of time under 80 ℃.
2, by electrospinning device, at voltage 18kV, spinning head and the receiving device feed flow velocity 3mL/h apart from 5cm, spinning solution, the spinning solution electrospinning prepares pitch/CuCl
2The composite nano fiber precursor.
3, with the pitch/CuCl for preparing
2The composite nano fiber precursor is dry 24h in vacuum drying chamber (vacuum is 0.04MPa, temperature 50 C).
4, dried pitch/CuCl
2The composite nano fiber precursor is at H
2/ N
2The lower 600 ℃ of calcining 5h of inert atmosphere.Prepare diameter at the C/Cu of 1000～2000nm scope composite nano fiber.
5, the C/Cu composite nano fiber is to process 48h under 80 ℃ of nitration mixture (nitric acid and sulfuric acid) in temperature, then at the dry 24h of vacuum drying chamber (vacuum is 150 ℃ of 0.01MPa, temperature), finally obtain hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber, wherein the diameter of hollow plumbago carbon nanometer bead is at 2～20nm, and the wall thickness of graphitic carbon is at 1～5nm.
6, prepare according to a conventional method li-ion electrode: take the preparation material with carbon element as working electrode, the lithium sheet is to electrode, Celgard 2400 is barrier film, with 1mol/L LiPF
6In EC: DMC: EMC (1: 1: 1 volume ratio) is electrolyte, is prepared into button cell.The test voltage scope is 0～3V.When current density is 50mA/g when carrying out abundant electric performance test, be 650mAhg than electric capacity
-1
Example seven
1, preparation electrostatic spinning solution: with 1.9g Kynoar, 0.6g ferrous acetate (Fe (Ac)
2) and 10g DMF mixing, the spinning solution of formation homogeneous after stirring a period of time under 50 ℃.
2, by electrospinning device, prepare Kynoar/Fe (Ac) at voltage 15kV, spinning head and receiving device apart from feed flow velocity 0.1mL/h, the above-mentioned spinning solution of tele-release of 20cm, spinning solution
2The composite nano fiber precursor.
3, with the Kynoar/Fe (Ac) for preparing
2The composite nano fiber precursor is dry 8h in vacuum drying chamber (vacuum is 90 ℃ of 0.04MPa, temperature).
4, dried Kynoar/Fe (Ac)
2The composite nano fiber precursor is at H
2/ N
2The lower 1000 ℃ of calcining 2h of inert atmosphere.Prepare diameter at the C/Fe of 200～1000nm scope composite nano fiber.
5, the C/Fe composite nano fiber is to process 48h under 25 ℃ of hydrochloric acid in temperature, then at the dry 24h of vacuum drying chamber (vacuum is 120 ℃ of 0.01MPa, temperature), finally obtain hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber, wherein the diameter of hollow plumbago carbon nanometer bead is at 50～100nm, and the wall thickness of graphitic carbon is at 20～60nm.
6, prepare according to a conventional method ultracapacitor: take the preparation material with carbon element as working electrode, Pt is to electrode, with 1mol/L N
2SO
4Or KOH solution is electrolyte, is assembled into the capacitor unit of sandwich structure.The test voltage scope is 0～0.9V.When current density is 500mA/g when carrying out abundant electric performance test, be 200Fg than capacitance
-1
Example eight
1, preparation electrostatic spinning solution: with 1g polyacrylonitrile (PAN), 0.5g polypyrrole (PPy), 1g copper nitrate Cu (NO
3)
2Mix with the 27mL dimethyl formamide, form the spinning solution of homogeneous after stirring a period of time under 80 ℃.
2, the electrospinning device by coaxial nozzle, be to carry out spinning under mineral oil (Oil), outer shaft polyacrylonitrile/polypyrrole/copper nitrate mixed liquor, voltage 17kV, spinning head and the receiving device condition apart from the feed flow velocity 0.3mL/h of 15cm, interior outer shaft at interior axle, preparation PAN/PPy/Cu (NO
3)
2The coaxial composite of@Oil.
3, with the PAN/PPy/Cu (NO for preparing
3)
2The coaxial composite precursor of@Oil is dry 4h in vacuum drying chamber (vacuum is 40 ℃ of 0.03MPa, temperature).
4, dried PAN/PPy/Cu (NO
3)
2The coaxial composite precursor of@Oil is at H
2/ N
2The lower 800 ℃ of calcining 2h of inert atmosphere.Prepare diameter at the C/Cu of 50～300nm scope composite nano tube, the diameter of pipe is 30～80nm.
5, the C/Cu composite nano tube is 40 ℃ in temperature, processes 48h under the mixed acid with nitric acid/sulfuric acid, then clean with distilled water, finally at the dry 24h of vacuum drying chamber (vacuum is 120 ℃ of 0.01MPa, temperature), finally obtain hollow plumbago carbon nanometer bead and modify the amorphous carbon nanotube, wherein the diameter of hollow plumbago carbon nanometer bead is at 60～100nm, and the wall thickness of graphitic carbon is at 40～100nm.
6, electrode assembling is pressed the described conventional method of embodiment 1 and is prepared and test, and when current density is 50mA/g when carrying out abundant electric performance test, is 700mAhg than electric capacity
-1
Example nine
1, preparation electrostatic spinning solution: with 0.5g poly(ethylene oxide) (PEO), 0.2g nickel nitrate (Ni (NO
3)
2) and the mixing of 10g deionized water, the spinning solution of formation homogeneous after stirring a period of time under 50 ℃.
2, by the electrospinning device of coaxial nozzle, be mineral oil (Oil), outer shaft PEO/Ni (NO at interior axle
3)
2Carry out spinning under mixed liquor, voltage 16kV, spinning head and the receiving device condition apart from the feed flow velocity 0.2mL/h of 18cm, interior outer shaft, preparation PEO/Ni (NO
3)
2The coaxial composite of@Oil.
3, with the PEO/Ni (NO for preparing
3)
2@Oil composite nano fiber precursor is dry 4h in vacuum drying chamber (vacuum is 40 ℃ of 0.04MPa, temperature).
4, dried PEO/Ni (NO
3)
2@Oil composite nano fiber precursor is at H
2/ Ar
2The lower 500 ℃ of calcining 3h of inert atmosphere.Prepare diameter at the C/Ni of 400～600nm scope composite nano tube, the diameter of pipe is 100～200nm.
5, the C/Ni composite nano tube is 25 ℃, use salt acid treatment 48h in temperature, then clean with distilled water, finally at the dry 48h of vacuum drying chamber (vacuum is 120 ℃ of 0.01MPa, temperature), finally obtain hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanotube, wherein the diameter of hollow plumbago carbon nanometer bead is at 5～20nm, and the wall thickness of graphitic carbon nano bead is at 2～6nm.
6, electrode assembling is pressed the described conventional method of embodiment 1 and is prepared and test, and when current density is 50mA/g when carrying out abundant electric performance test, is 630mAhg than electric capacity
-1
Example ten
1, preparation electrostatic spinning solution: with 2.2g polymethyl methacrylate (PMMA), 1g iron chloride (FeCl
3) and the mixing of 10mL dimethyl formamide, the spinning solution of formation homogeneous after stirring a period of time under 50 ℃.In addition, the polyvinylpyridine alkane ketone (PVP) with 1g is dissolved in the 20mL dimethyl formamide.
2, by the electrospinning device of three coaxial nozzles, be mineral oil (Oil), axis PMMA/FeCl at interior axle
3Mixed liquor, outer shaft are to carry out spinning under PVP solution, voltage 17kV, spinning head and the receiving device condition apart from the feed flow velocity 0.01mL/h of 20cm, interior outer shaft, preparation PVP/PMMA/FeCl
3@Oil composite.
3, with the PVP/PMMA/FeCl for preparing
3@Oil composite nano fiber precursor is dry 4h in vacuum drying chamber (vacuum is 40 ℃ of 0.04MPa, temperature).
4, dried PVP/PMMA/FeCl
3@Oil composite nano fiber precursor is at H
2/ Ar
2The lower 1000 ℃ of calcining 2h of inert atmosphere.Prepare diameter at the C/Fe of 700～1000nm scope composite nano tube, the diameter of pipe is 300nm.
5, the C/Fe composite nano tube is 30 ℃, processes 48h with nitration mixture (nitric acid and hydrochloric acid) in temperature, then clean with distilled water, finally at the dry 24h of vacuum drying chamber (vacuum is 130 ℃ of 0.01MPa, temperature), finally obtain hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanotube, wherein the diameter of hollow plumbago carbon nanometer bead is at 5～40nm, and the wall thickness of graphitic carbon nano bead is at 1～7nm.
6, electrode assembling is pressed the described conventional method of embodiment 1 and is prepared and test, and when current density is 50mA/g when carrying out abundant electric performance test, is 700mAhg than electric capacity
-1
Claims (11)
1. the preparation method of a hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or CNT, is characterized in that, sequentially comprises the steps:
(1) preparation electrostatic spinning liquid: but be mixed with uniform electrostatic spinning liquid with polar solvent with after transition metal salt and cyclisation macromolecule resin mix and blend, but wherein but the macromolecule resin of cyclisation described in electrostatic spinning liquid accounts for 5 ~ 50% of described cyclisation macromolecule resin and polar solvent quality sum; But described transition metal salt accounts for 0.5 ~ 50 % of described cyclisation macromolecule resin and polar solvent quality sum;
(2) preparation of composite nano fiber precursor: with the electrostatic spinning liquid of step (1) preparation by electrospinning device under the high-pressure electrostatic effect, be prepared into the composite nano fiber precursor;
(3) drying: described composite nano fiber precursor is dry in a vacuum;
(4) calcining: the carbonization in inert atmosphere of dried composite nano fiber precursor is become composite nano fiber or nanotube;
(5) acid treatment and dry: the composite nano fiber after carbonization or nanotube are processed with acid, and drying makes described hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or CNT in a vacuum.
2. the preparation method of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber according to claim 1 or CNT, it is characterized in that, described step (1) but in the described cyclisation macromolecule resin that adopts comprise: one or more combinations in Kynoar, polyvinyl alcohol, pitch, polypyrrole, polyvinylpyridine alkane ketone, poly(ethylene oxide), polymethyl methacrylate, PLA, polyacrylonitrile and polystyrene.
3. the preparation method of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber according to claim 1 or CNT, it is characterized in that, the transition metal salt that adopts in described step (1) comprises: one or more combinations in Schweinfurt green, copper chloride, copper sulphate, copper carbonate, nickel acetate, nickel chloride, nickelous carbonate, nickelous sulfate, ferric acetate and iron chloride.
4. the preparation method of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber according to claim 1 or CNT, it is characterized in that, the polar solvent that adopts in described step (1) is one or more combinations in water, ethanol, dimethyl formamide, oxolane, acetone and dimethyl sulfoxide (DMSO).
5. the preparation method of the described hollow plumbago carbon of any one nanometer bead in-situ modification amorphous carbon nanofiber/CNT according to claim 1-4, it is characterized in that, in described step (2), the electrospinning parameter is: voltage 9 ~ 25 kV, collection distance are that 5 ~ 20 cm, feeding speed are 0.01 ~ 1 mL/h; Wherein the nozzle of electrospinning device is single shaft, coaxial or three coaxial.
6. the preparation method of the described hollow plumbago carbon of any one nanometer bead in-situ modification amorphous carbon nanofiber or CNT according to claim 1-4, it is characterized in that, described in described step (3), the dry environment of composite nano fiber precursor is: vacuum is dry 1 ~ 24 h under 0.04 ~ 0.01 MPa, 40 ~ 90 ° of C of temperature; Described in described step (5), composite nano fiber or nanotube at the dry environment after acid treatment are: vacuum is dry 1 ~ 48 h under 0.04 ~ 0.005 MPa, 40 ~ 200 ° of C of temperature.
7. the preparation method of the described hollow plumbago carbon of any one nanometer bead in-situ modification amorphous carbon nanofiber or CNT according to claim 1-4, it is characterized in that, in described step (4), dried composite nano fiber precursor calcined 1 ~ 20 h in calcining heat under inert atmosphere protection under 400 ~ 1000 ° of C and form composite nano fiber or the nanotube of carbonization; Wherein said inert gas can be nitrogen, argon gas, hydrogen/argon gas composite gas, hydrogen/nitrogen composite gas.
8. the preparation method of the described hollow plumbago carbon of any one nanometer bead in-situ modification amorphous carbon nanofiber or CNT according to claim 1-4, it is characterized in that, nanofiber or nanotube acidic treatment at 20 ~ 80 ° of C temperature of carbonization after calcining in described step (5), one or more combinations in nitric acid, sulfuric acid, hydrofluoric acid and hydrochloric acid are adopted in wherein said acid.
9. the preparation method of any one makes in one kind according to claim 1-8 hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or CNT, it is characterized in that, its pattern is a kind of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or a kind of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanotube, the diameter of wherein said hollow plumbago carbon nanometer bead 2 ~ 100 nm and wherein the thickness of graphitic carbon at 1 ~ 100 nm; The diameter of described carbon nano-fiber is at 50 ~ 2000 nm, and perhaps the diameter of described CNT is at 50 ~ 2500 nm, and the pipe diameter of CNT is at 30 ~ 600 nm.
10. an electrode, is characterized in that, described electrode is assembled by following material: hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or CNT that according to claim 1-8, the preparation method of any one makes.
11. a lithium ion battery or ultracapacitor is characterized in that having electrode according to claim 10, the reversible capacity of wherein said lithium ion battery is 400～1100 mAhg
-1The reversible capacity of described ultracapacitor is 70～200 F/g.
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| CN103928239A (en) * | 2014-05-06 | 2014-07-16 | 吉林大学 | Surface modification method of supercapacitor electrode material active carbon fibers |
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| CN106531450A (en) * | 2016-10-31 | 2017-03-22 | 安徽江威精密制造有限公司 | Electrostatic spinning composite electrode material with added copper nitrate-modified active carbon |
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| CN112174131A (en) * | 2020-10-10 | 2021-01-05 | 福建师范大学 | Method for preparing graphitized hollow carbon composite material by dynamic catalytic wide-area graphitization |
| CN112357906A (en) * | 2020-11-12 | 2021-02-12 | 同济大学 | Nitrogen-doped monomodal ultramicropore carbon nanosheet synthesized by in-situ amorphous cobalt template method, and method and application thereof |
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