CN103088465B - 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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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 189
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 102
- 239000010439 graphite Substances 0.000 title claims abstract description 69
- 229910003481 amorphous carbon Inorganic materials 0.000 title claims abstract description 56
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 54
- 238000012986 modification Methods 0.000 title claims abstract description 53
- 230000004048 modification Effects 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 18
- 239000000835 fiber Substances 0.000 title abstract description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 title abstract description 5
- 229910002804 graphite Inorganic materials 0.000 title abstract 3
- 239000002131 composite material Substances 0.000 claims abstract description 93
- 239000002243 precursor Substances 0.000 claims abstract description 44
- 229920002521 macromolecule Polymers 0.000 claims abstract description 37
- 239000002071 nanotube Substances 0.000 claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003763 carbonization Methods 0.000 claims abstract description 15
- 238000010306 acid treatment Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 5
- 241000209456 Plumbago Species 0.000 claims description 66
- 239000011324 bead Substances 0.000 claims description 63
- 239000002121 nanofiber Substances 0.000 claims description 63
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 56
- 239000002134 carbon nanofiber Substances 0.000 claims description 54
- 229920005989 resin Polymers 0.000 claims description 39
- 239000011347 resin Substances 0.000 claims description 39
- -1 transition metal salt Chemical class 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- 229910052723 transition metal Inorganic materials 0.000 claims description 29
- 238000010041 electrostatic spinning Methods 0.000 claims description 27
- 238000001523 electrospinning Methods 0.000 claims description 23
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000002798 polar solvent Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 9
- 229920000128 polypyrrole Polymers 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000002441 reversible effect Effects 0.000 claims description 6
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000009987 spinning Methods 0.000 abstract description 38
- 230000006378 damage Effects 0.000 abstract 1
- 238000005087 graphitization Methods 0.000 abstract 1
- 238000007363 ring formation reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 23
- 238000001291 vacuum drying Methods 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000010949 copper Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 238000007796 conventional method Methods 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000002480 mineral oil Substances 0.000 description 8
- 235000010446 mineral oil Nutrition 0.000 description 8
- 239000002086 nanomaterial Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002102 nanobead Substances 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
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, new forms of energy, economize energy technology, the exploitation of Environmental Technology and the utilization of comprehensive high-efficiency have become to attach most importance to middle heavy problem.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 meet the requirements such as high power, high life, high stability.Current material with carbon element due to low price, nontoxic, stablize high receive society favor.The such as main material such as current commercial lithium ion battery and ultracapacitor is exactly material with carbon element composition.But because material with carbon element structural constraint the development of high power capacity, therefore improve material with carbon element capacity extremely urgent.
The nanometer of material imparts the higher performance of material, even New function.Carbon nanomaterial is owing to having high-specific surface area, and the ability of absorption electrolyte intermediate ion improves, thus improves the capacity of material with carbon element.At present, a series of synthetic technology successfully prepares various carbon nanomaterial, such as: chemical method, calcining technology, collosol and gel etc.The setting of parameter determines structure and the performance thereof of end product.Therefore, the ability controlling to have a high performance product is the final purpose for any one preparation method.These methods relatively, electrostatic spinning technique is under action of high voltage, electric field force overcomes the surface tension of solution, hemispherical droplet becomes taper (Taylor cone), and then charged jet can overcome the surface tension of solution from " taper (Taylor cone) " injection, and then unordered arrival receiving device forms fiber web.Compared with other method, electrostatic spinning process is simple, can the features such as continuous production, expense be not high and efficient, the more important thing is that its in-situ modification ability is high, can industrialization, be considered to prepare the best approach of nano material, the nanofiber of preparation/manage its diameter 10nm ~ 10 μm.Electrostatic spinning technique of the present invention below Here it is.
Carbon nano-fiber/CNT has the design feature of nano material, compares with traditional material with carbon element (graininess), has that specific area is large, chemism high.Although carbon nano-fiber/CNT can improve the capacity of ultracapacitor and lithium ion battery, how further raising capacity and stability thereof still govern the application of carbon nano-fiber/CNT.Such as: when carbon nano-fiber/CNT is applied in lithium ion battery, it is fast that owing to not having the volumetric expansion brought in unnecessary spatial stability charge and discharge process to cause, its stability is low, capacity declines; In addition, carbon nano-fiber/nanotube stores electrolyte ion to improve its capacity as needing very large specific area to go during ultracapacitor.Therefore prepare a kind of novelty, high power capacity, high stability, the carbon nano-fiber/CNT of high life be the difficult problem that numerous researcher goes all out to capture.
Summary of the invention
The technical problem to be solved in the present invention is, space for the existing carbon nano-fiber/CNT defect that to cause that stability is low, capacity declines not fast, 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 prepared by 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 field such as lithium ion battery and ultracapacitor.
Adopt technical scheme as follows for realizing object of the present invention: the preparation method that the invention provides a kind of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or CNT, sequentially comprises the steps:
(1) prepare electrostatic spinning liquid: with polar solvent by transition metal salt with can be mixed with uniform electrostatic spinning liquid after cyclisation macromolecule resin mix and blend, wherein described in electrostatic spinning liquid can cyclisation macromolecule resin account for described can cyclisation macromolecule resin and polar solvent quality sum 5 ~ 50%; Described transition metal salt account for described can cyclisation macromolecule resin and polar solvent quality sum 0.5 ~ 50%;
(2) preparation of composite nano fiber precursor: electrostatic spinning liquid step (1) prepared under high-pressure electrostatic effect, is prepared into composite nano fiber precursor by electrospinning device;
(3) dry: by dry in a vacuum for described composite nano fiber precursor;
(4) calcine: by dried composite nano fiber precursor in an inert atmosphere carbonization become composite nano fiber or nanotube;
(5) acid treatment is also dry: the composite nano fiber after carbonization or nanotube acid are processed, and drying obtains described hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or CNT in a vacuum.
According in the preparation method of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber of the present invention or CNT, what adopt in described step (1) describedly can comprise by cyclisation macromolecule resin: one or more combinations in Kynoar, polyvinyl alcohol, pitch, polypyrrole, polyvinylpyridine alkane ketone, poly(ethylene oxide), polymethyl methacrylate, PLA, polyacrylonitrile and polystyrene.
According in the preparation method of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber of the present invention or CNT, the transition metal salt adopted 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.
According in the preparation method of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber of the present invention or CNT, the polar solvent adopted in described step (1) is one or more combinations in water, ethanol, dimethyl formamide, oxolane, acetone and dimethyl sulfoxide (DMSO).
According in the preparation method of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber of the present invention or CNT, in described step (2), electrospinning parameter is: voltage 9 ~ 25kV, collection distance are 5 ~ 20cm, feeding speed is 0.01 ~ 1mL/h; Wherein the nozzle of electrospinning device is single shaft, coaxial or three coaxial.
According in the preparation method of 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 at 0.04 ~ 0.01MPa, temperature 40 ~ 90 DEG C; Composite nano fiber described in described step (5) or the dry environment of nanotube after acid treatment are: vacuum is dry 1 ~ 48h at 0.04 ~ 0.005MPa, temperature 40 ~ 200 DEG C.
According in the preparation method of 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 calcining heat under inert atmosphere protection calcined 1 ~ 20h at 400 ~ 1000 DEG 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.
According in the preparation method of hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber of the present invention or CNT, by the nanofiber of carbonization after calcining or nanotube acidic treatment at 20 ~ 80 DEG C of temperature in described step (5), wherein said acid adopts one or more combinations in nitric acid, sulfuric acid, hydrofluoric acid and hydrochloric acid.
Present invention also offers hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or CNT that a kind of preparation method as above obtains, 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 at 2 ~ 100nm and wherein the thickness of graphitic carbon at 1 ~ 100nm; The diameter of described carbon nano-fiber is at 50 ~ 2000nm, or the diameter of described CNT is at 50 ~ 2500nm, and the pipe diameter of CNT is at 30 ~ 600nm.
Present invention also offers a kind of electrode, described electrode is assembled by following material: the hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber obtained according to preparation method as above or CNT.
Present invention also offers a kind of lithium ion battery or ultracapacitor, have according to electrode as above, the reversible capacity of wherein said lithium ion battery is 400 ~ 1100mAhg
-1; The 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, there is following beneficial effect:
(1) the hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber/carbon nano tube structure prepared of the present invention is novel, specific area is large, space is many, conductance is high, the ability to structural deterioration that opposing outside cause causes volumetric expansion to bring is good, easy recovery, 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 prepared by 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 field 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.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearly understand, the present invention is further elaborated.
According to the difference of preparation condition in carbon nanomaterial prepared by the inventive method, 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, be made up of at the CNT of 50 ~ 2500nm at the carbon nano-fiber of 50 ~ 2000nm or diameter at the hollow plumbago carbon nanometer bead (wherein the thickness of graphitic carbon is at 1 ~ 100nm) of 2 ~ 100nm and diameter diameter, wherein the caliber of CNT is at 30 ~ 600nm.
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) prepare electrostatic spinning liquid: with can under agitation by transition metal salt with can the cyclisation macromolecule resin polar solvent that stirs into uniform state by transition metal salt with can be mixed with uniform electrostatic spinning liquid after cyclisation macromolecule resin mix and blend, wherein in electrostatic spinning liquid can the percentage by weight of cyclisation macromolecule resin and transition metal salt as follows: can cyclisation macromolecule resin account for can cyclisation macromolecule resin and polar solvent quality sum 5 ~ 50%; Transition metal salt account for can cyclisation high-molecular resin solution quality 1 ~ 50%.Wherein can refer to by can cyclisation macromolecule resin and polar solvent form by cyclisation high-molecular resin solution.Therefore, above-mentionedly can to refer to and can account for the percentage that can spin macromolecule resin and polar solvent sum by cyclisation macromolecule resin by cyclisation macromolecule resin percentage by weight.The percentage of transition metal salt refers to that transition metal salt accounts for can the percentage of cyclisation high-molecular resin solution.Of the present inventionly can refer to that macromolecule resin is under inert gas shielding by cyclisation macromolecule resin, 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 high-pressure electrostatic effect, prepares composite nano fiber precursor by electrospinning device;
(3) dry: composite nano fiber precursor is dry in a vacuum;
(4) calcine: 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 is also dry: the composite nano fiber of acquisition or nanotube are used acid treatment at a certain temperature; Acid-treated composite nano fiber or nanotube drying are obtained described hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or CNT.
When this carbon nanomaterial is prepared into electrode by needs, then again by step (6): prepare electrode and the carbon nano-fiber after dried acid treatment or CNT are assembled into electrode.And further based on this electrode, lithium ion battery provided by the invention or ultracapacitor can be assembled into.
In above-mentioned preparation process; wherein can refer under inert gas shielding by cyclisation macromolecule resin in step (1); can can cyclisation and produce the macromolecule resin of material with carbon element in high temperature cabonization process, 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; transition metal is formed at high-temperature calcination late transition metal salt; and catalysis the carbonization of cyclisation macromolecule resin can become graphited carbon in this process, one or more combinations of such as Schweinfurt green, copper chloride, copper sulphate, copper carbonate, nickel acetate, nickel chloride, nickelous carbonate, nickelous sulfate, ferric acetate, iron chloride etc.Described polar solvent refer to by stir by transition metal salt with can stir into uniform polar solvent by cyclisation macromolecule resin, the present invention chooses one or more combinations of water, ethanol and dimethyl formamide, oxolane, acetone and dimethyl sulfoxide (DMSO).Certainly other can cyclisation macromolecule, can rise catalysis transition metal salt, transition metal salt can be dissolved simultaneously and can the solvent of material of cyclisation macromolecule resin also can use, this is that those skilled in the art can be found by limited number of time test.Thus all can cyclisation macromolecule resin, can rise catalytic action transition metal salt, can dissolve transition metal salt with can the solvent of 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), composite nano fiber precursor is by electrospinning device, is: voltage 9 ~ 25kV, collection distance are 5 ~ 20cm, feeding speed is 0.01 ~ 1mL/h in electrospinning parameter.Wherein the nozzle of electrospinning device can be single shaft, coaxial and three coaxial.When wherein preparing hollow plumbago carbon in-situ modification amorphous carbon nanofiber with single shaft nozzle, spinning solution is can 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, and the spinning solution of outer shaft is can the mixed solution of cyclisation macromolecule resin and transition metal salt.Preparing interior axle when hollow plumbago carbon modifies amorphous carbon nanotube with three axles is mineral oil or vegetable oil, and jackshaft is can the mixed solution of cyclisation macromolecule resin and transition metal salt, and outer shaft is can cyclisation high-molecular resin solution; Or jackshaft is can cyclisation high-molecular resin solution, outer shaft is can the mixed solution of cyclisation macromolecule resin and transition metal salt.It is also passable that other combinations certain finally can prepare hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber/CNT.
Wherein in step (3), composite nano fiber precursor is dry 1 ~ 24h at vacuum is 0.04 ~ 0.01MPa, temperature 40 ~ 90 DEG C.Nanofiber/the nanotube of the carbonization in step (5) after acid treatment is dry 1 ~ 48h at vacuum is 0.04 ~ 0.005MPa, temperature 40 ~ 200 DEG C.
Wherein in step (4), dried composite nano fiber precursor calcining heat under inert atmosphere protection is calcined at 400 ~ 1000 DEG C 1 ~ 20h and form carbonization composite nano fiber/nanotube.Wherein inert gas can be nitrogen, argon gas, hydrogen/argon gas composite gas, hydrogen/nitrogen composite gas.In addition by calcining after carbonization after composite nano fiber/nanotube acidic treatment at 20 ~ 80 DEG C of temperature, as long as wherein can by transition metal dissolution acid out can, such as nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid one or more combination.
Electrode prepared by the present invention can be the electrode of lithium ion battery, also can be 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, the present invention adopts transition metal salt to be raw material, and utilizing electrostatic spinning technique to be evenly distributed on can in the macromolecule resin of cyclisation, by the carbonization under an inert atmosphere of electrospinning composite fibre.At this moment transition metal salt resolves into transition metal nanoparticles, under its catalytic action, carbonization is become graphited carbon by the carbon of transiting metal surface, then after acid treatment, forms the amorphous carbon nano-fiber/CNT of a kind of hollow plumbago carbon nanometer bead in-situ modification.The in-situ preparation hollow plumbago carbon nanometer bead that this invention proposes is modified amorphous carbon nano-fiber/CNT and preparation method thereof and is overcome cyclisation macromolecule and need the graphited shortcoming of high-temperature, achieve the amorphous carbon nano-fiber/CNT of hollow plumbago carbon nanometer bead in-situ modification, improve the specific area of composite nano fiber/nanotube simultaneously, electrical conductivity, and the ability to structural deterioration that opposing outside cause causes volumetric expansion to bring.The electrode be made up of 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, stability high, in the field such as high performance lithium ion battery and ultracapacitor, there is important application prospect.
The present invention is described according to specific embodiment, but it will be understood by those skilled in the art that when not departing from the scope of the invention, can carry out various change and equivalent replacement.In addition, for adapting to specific occasion or the material of the technology of the present invention, can many amendments be carried out to the present invention and not depart from its protection domain.Therefore, the present invention is not limited to specific embodiment disclosed herein, and comprises all embodiments dropping into claims.
Example one
1, electrostatic spinning solution is prepared: with 7.5g polyvinyl alcohol (PVA), 4g nickel chloride (NiCl
2) and the mixing of 67.5mL distilled water, form homogeneous spinning solution stir a period of time at 80 DEG C after.
2, by electrospinning device, at the feed flow velocity 0.4mL/h of voltage 20kV, spinning head and receiving device distance 18cm, spinning solution, spinning solution electrospinning prepares PVA/NiCl
2composite nano fiber precursor.
3, by the PVA/NiCl of preparation
2composite nano fiber precursor is dry 8h in vacuum drying chamber (vacuum is 0.03MPa, temperature 70 C).
4, dried PVA/NiCl
2composite nano fiber precursor is at H
2/ N
2the lower 500 DEG C of calcining 2h of inert atmosphere.Prepare the C/Ni composite nano fiber of diameter in 50 ~ 100nm scope.
5, C/Ni composite nano fiber processes 48h under temperature is 30 DEG C of nitric acid, then at vacuum drying chamber (vacuum is 0.01MPa, temperature 150 DEG C) dry 24h, 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 li-ion electrode according to a conventional method: with the material with carbon element prepared for working electrode, lithium sheet is to electrode, and 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.Test voltage scope is 0 ~ 3V.When current density be 50mA/g carry out abundant electric performance test time, ratio capacitance is 550mAhg
-1.
Example two
1, electrostatic spinning solution is prepared: with 2.5g PVA, 1.5g nickel acetate (Ni (Ac)
2) and the mixing of 22.5mL distilled water, form homogeneous spinning solution stir a period of time at 80 DEG C after.
2, by electrospinning device, PVA/Ni (Ac) is prepared at the feed flow velocity 0.5mL/h of voltage 17kV, spinning head and receiving device distance 18cm, spinning solution, the above-mentioned spinning solution of tele-release
2composite nano fiber precursor.
3, by the PVA/Ni (Ac) of preparation
2composite nano fiber precursor is dry 8h in vacuum drying chamber (vacuum is 0.02MPa, temperature 70 C).
4, dried PVA/Ni (Ac)
2composite nano fiber precursor is at N
2the lower 500 DEG C of calcining 2h of inert atmosphere.Prepare the C/Ni composite nano fiber of diameter in 50 ~ 200nm scope.
5, C/Ni composite nano fiber processes 48h under temperature is 25 DEG C of hydrochloric acid, then at vacuum drying chamber (vacuum is 0.01MPa, temperature 120 DEG C) dry 24h, 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 ultracapacitor according to a conventional method: with the material with carbon element prepared for working electrode, Pt is to electrode, with 1mol/L N
2sO
4or KOH solution is electrolyte, be assembled into the capacitor unit of sandwich structure.Test voltage scope is 0 ~ 0.9V.When current density be 500mA/g carry out abundant electric performance test time, ratio capacitance value is 80Fg
-1.
Example three
1, electrostatic spinning solution is prepared: 1g polystyrene (PS), 0.5g Schweinfurt green (Cu (Ac)
2) and the mixing of 10mL dimethyl formamide, form homogeneous spinning solution stir a period of time at 80 DEG C after.
2, by the electrospinning device of coaxial nozzle, be mineral oil (Oil), outer shaft PS/Cu (Ac) at interior axle
2spinning is carried out, preparation PS/Cu (Ac) under the condition of the feed flow velocity 0.3mL/h of mixed liquor, voltage 17kV, spinning head and receiving device distance 20cm, interior outer shaft
2the coaxial composite of@Oil.
3, by the PS/Cu (Ac) of preparation
2@Oil coaxial composite precursor is dry 4h in vacuum drying chamber (vacuum is 0.03MPa, temperature 40 DEG C).
4, dried PS/Cu (Ac)
2the coaxial composite precursor of@Oil is at H
2/ N
2the lower 500 DEG C of calcining 2h of inert atmosphere.Prepare the C/Cu composite nano tube of diameter in 200 ~ 300nm scope, the diameter of pipe is 30 ~ 80nm.
5, C/Cu composite nano tube is 40 DEG C in temperature, processes 48h with under the mixed acid of nitric acid/sulfuric acid, then clean with distilled water, final at vacuum drying chamber (vacuum is 0.01MPa, temperature 120 DEG C) dry 24h, finally obtain hollow plumbago carbon nanometer bead and modify 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 prepared by the conventional method described in embodiment 1 and tests, when current density be 50mA/g carry out abundant electric performance test time, ratio capacitance is 560mAhg
-1.
Example four
1, electrostatic spinning solution is prepared: with 1g polyacrylonitrile (PAN), 1g nickel chloride (NiCl
2) and the mixing of 17mL dimethyl formamide, form homogeneous spinning solution stir a period of time at 50 DEG C after.
2, by the electrospinning device of coaxial nozzle, be mineral oil (Oil), outer shaft PAN/NiCl at interior axle
2spinning is carried out, preparation PAN/NiCl under the condition of the feed flow velocity 0.2mL/h of mixed liquor, voltage 16kV, spinning head and receiving device distance 18cm, interior outer shaft
2the coaxial composite of@Oil.
3, by the PAN/NiCl of preparation
2@Oil composite nano fiber precursor is dry 4h in vacuum drying chamber (vacuum is 0.04MPa, temperature 40 DEG C).
4, dried PAN/NiCl
2@Oil composite nano fiber precursor is at H
2/ Ar
2the lower 600 DEG C of calcining 3h of inert atmosphere.Prepare the C/Ni composite nano tube of diameter in 200 ~ 300nm scope, the diameter of pipe is 30 ~ 80nm.
5, C/Ni composite nano tube is 25 DEG C in temperature, uses HCl treatment 48h, then clean with distilled water, final at vacuum drying chamber (vacuum is 0.01MPa, temperature 120 DEG C) dry 48h, 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 prepared by the conventional method described in embodiment 1 and tests, when current density be 50mA/g carry out abundant electric performance test time, ratio capacitance is 546mAhg
-1.
Example five
1, electrostatic spinning solution is prepared: with 1g polyacrylonitrile (PAN), 1g nickel chloride (NiCl
2) and the mixing of 17mL dimethyl formamide, form homogeneous spinning solution stir a period of time at 50 DEG C after.In addition, the polyvinylpyridine alkane ketone (PVP) of 1g is dissolved in 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 PVP solution, voltage 17kV, spinning head and receiving device distance 20cm, interior outer shaft feed flow velocity 0.01mL/h condition under carry out spinning, preparation PVP/PAN/NiCl
2@Oil composite.
3, by the PVP/PAN/NiCl of preparation
2@Oil composite nano fiber precursor is dry 4h in vacuum drying chamber (vacuum is 0.04MPa, temperature 40 DEG C).
4, dried PVP/PAN/NiCl
2@Oil composite nano fiber precursor is at H
2/ Ar
2the lower 600 DEG C of calcining 2h of inert atmosphere.Prepare the C/Ni composite nano tube of diameter in 100 ~ 300nm scope, the diameter of pipe is 70nm.
5, C/Ni composite nano tube is 30 DEG C in temperature, processes 48h with nitration mixture (nitric acid and hydrochloric acid), then clean with distilled water, final at vacuum drying chamber (vacuum is 0.01MPa, temperature 130 DEG C) dry 24h, 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 prepared by the conventional method described in embodiment 1 and tests, when current density be 50mA/g carry out abundant electric performance test time, ratio capacitance is 700mAhg
-1.
Example six
1, electrostatic spinning solution is prepared: with 4.5g pitch, 0.5g copper chloride (CuCl
2) and the mixing of 10g oxolane, form homogeneous spinning solution stir a period of time at 80 DEG C after.
2, by electrospinning device, at the feed flow velocity 3mL/h of voltage 18kV, spinning head and receiving device distance 5cm, spinning solution, spinning solution electrospinning prepares pitch/CuCl
2composite nano fiber precursor.
3, by the pitch/CuCl of preparation
2composite nano fiber precursor is dry 24h in vacuum drying chamber (vacuum is 0.04MPa, temperature 50 C).
4, dried pitch/CuCl
2composite nano fiber precursor is at H
2/ N
2the lower 600 DEG C of calcining 5h of inert atmosphere.Prepare the C/Cu composite nano fiber of diameter in 1000 ~ 2000nm scope.
5, C/Cu composite nano fiber processes 48h under temperature is 80 DEG C of nitration mixture (nitric acid and sulfuric acid), then at vacuum drying chamber (vacuum is 0.01MPa, temperature 150 DEG C) dry 24h, 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 li-ion electrode according to a conventional method: with the material with carbon element prepared for working electrode, lithium sheet is to electrode, and 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.Test voltage scope is 0 ~ 3V.When current density be 50mA/g carry out abundant electric performance test time, ratio capacitance is 650mAhg
-1.
Example seven
1, electrostatic spinning solution is prepared: with 1.9g Kynoar, 0.6g ferrous acetate (Fe (Ac)
2) and 10g DMF mix, form homogeneous spinning solution stir a period of time at 50 DEG C after.
2, by electrospinning device, Kynoar/Fe (Ac) is prepared at the feed flow velocity 0.1mL/h of voltage 15kV, spinning head and receiving device distance 20cm, spinning solution, the above-mentioned spinning solution of tele-release
2composite nano fiber precursor.
3, by the Kynoar/Fe (Ac) of preparation
2composite nano fiber precursor is dry 8h in vacuum drying chamber (vacuum is 0.04MPa, temperature 90 DEG C).
4, dried Kynoar/Fe (Ac)
2composite nano fiber precursor is at H
2/ N
2the lower 1000 DEG C of calcining 2h of inert atmosphere.Prepare the C/Fe composite nano fiber of diameter in 200 ~ 1000nm scope.
5, C/Fe composite nano fiber processes 48h under temperature is 25 DEG C of hydrochloric acid, then at vacuum drying chamber (vacuum is 0.01MPa, temperature 120 DEG C) dry 24h, 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 ultracapacitor according to a conventional method: with the material with carbon element prepared for working electrode, Pt is to electrode, with 1mol/L N
2sO
4or KOH solution is electrolyte, be assembled into the capacitor unit of sandwich structure.Test voltage scope is 0 ~ 0.9V.When current density be 500mA/g carry out abundant electric performance test time, ratio capacitance value is 200Fg
-1.
Example eight
1, electrostatic spinning solution is prepared: with 1g polyacrylonitrile (PAN), 0.5g polypyrrole (PPy), 1g copper nitrate Cu (NO
3)
2with the mixing of 27mL dimethyl formamide, stir a period of time at 80 DEG C after, form homogeneous spinning solution.
2, by the electrospinning device of coaxial nozzle, interior axle be mineral oil (Oil), outer shaft polyacrylonitrile/polypyrrole/copper nitrate mixed liquor, voltage 17kV, spinning head and receiving device distance 15cm, interior outer shaft feed flow velocity 0.3mL/h condition under carry out spinning, preparation PAN/PPy/Cu (NO
3)
2the coaxial composite of@Oil.
3, by the PAN/PPy/Cu (NO of preparation
3)
2@Oil coaxial composite precursor is dry 4h in vacuum drying chamber (vacuum is 0.03MPa, temperature 40 DEG C).
4, dried PAN/PPy/Cu (NO
3)
2the coaxial composite precursor of@Oil is at H
2/ N
2the lower 800 DEG C of calcining 2h of inert atmosphere.Prepare the C/Cu composite nano tube of diameter in 50 ~ 300nm scope, the diameter of pipe is 30 ~ 80nm.
5, C/Cu composite nano tube is 40 DEG C in temperature, processes 48h with under the mixed acid of nitric acid/sulfuric acid, then clean with distilled water, final at vacuum drying chamber (vacuum is 0.01MPa, temperature 120 DEG C) dry 24h, finally obtain hollow plumbago carbon nanometer bead and modify 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 prepared by the conventional method described in embodiment 1 and tests, when current density be 50mA/g carry out abundant electric performance test time, ratio capacitance is 700mAhg
-1.
Example nine
1, electrostatic spinning solution is prepared: with 0.5g poly(ethylene oxide) (PEO), 0.2g nickel nitrate (Ni (NO
3)
2) and the mixing of 10g deionized water, form homogeneous spinning solution stir a period of time at 50 DEG C after.
2, by the electrospinning device of coaxial nozzle, be mineral oil (Oil), outer shaft PEO/Ni (NO at interior axle
3)
2spinning is carried out, preparation PEO/Ni (NO under the condition of the feed flow velocity 0.2mL/h of mixed liquor, voltage 16kV, spinning head and receiving device distance 18cm, interior outer shaft
3)
2the coaxial composite of@Oil.
3, by the PEO/Ni (NO of preparation
3)
2@Oil composite nano fiber precursor is dry 4h in vacuum drying chamber (vacuum is 0.04MPa, temperature 40 DEG C).
4, dried PEO/Ni (NO
3)
2@Oil composite nano fiber precursor is at H
2/ Ar
2the lower 500 DEG C of calcining 3h of inert atmosphere.Prepare the C/Ni composite nano tube of diameter in 400 ~ 600nm scope, the diameter of pipe is 100 ~ 200nm.
5, C/Ni composite nano tube is 25 DEG C in temperature, uses HCl treatment 48h, then clean with distilled water, final at vacuum drying chamber (vacuum is 0.01MPa, temperature 120 DEG C) dry 48h, 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 prepared by the conventional method described in embodiment 1 and tests, when current density be 50mA/g carry out abundant electric performance test time, ratio capacitance is 630mAhg
-1.
Example ten
1, electrostatic spinning solution is prepared: with 2.2g polymethyl methacrylate (PMMA), 1g iron chloride (FeCl
3) and the mixing of 10mL dimethyl formamide, form homogeneous spinning solution stir a period of time at 50 DEG C after.In addition, the polyvinylpyridine alkane ketone (PVP) of 1g is dissolved in 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 PVP solution, voltage 17kV, spinning head and receiving device distance 20cm, interior outer shaft feed flow velocity 0.01mL/h condition under carry out spinning, preparation PVP/PMMA/FeCl
3@Oil composite.
3, by the PVP/PMMA/FeCl of preparation
3@Oil composite nano fiber precursor is dry 4h in vacuum drying chamber (vacuum is 0.04MPa, temperature 40 DEG C).
4, dried PVP/PMMA/FeCl
3@Oil composite nano fiber precursor is at H
2/ Ar
2the lower 1000 DEG C of calcining 2h of inert atmosphere.Prepare the C/Fe composite nano tube of diameter in 700 ~ 1000nm scope, the diameter of pipe is 300nm.
5, C/Fe composite nano tube is 30 DEG C in temperature, processes 48h with nitration mixture (nitric acid and hydrochloric acid), then clean with distilled water, final at vacuum drying chamber (vacuum is 0.01MPa, temperature 130 DEG C) dry 24h, 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 prepared by the conventional method described in embodiment 1 and tests, when current density be 50mA/g carry out abundant electric performance test time, ratio capacitance is 700mAhg
-1.
Claims (8)
1. a preparation method for hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or CNT, is characterized in that, sequentially comprise the steps:
(1) prepare electrostatic spinning liquid: with polar solvent by transition metal salt with can be mixed with uniform electrostatic spinning liquid after cyclisation macromolecule resin mix and blend, wherein described in electrostatic spinning liquid can cyclisation macromolecule resin account for described can cyclisation macromolecule resin and polar solvent quality sum 5 ~ 50%; Described transition metal salt account for described can cyclisation macromolecule resin and polar solvent quality sum 0.5 ~ 50%;
(2) preparation of composite nano fiber precursor: electrostatic spinning liquid step (1) prepared under high-pressure electrostatic effect, is prepared into composite nano fiber precursor by electrospinning device;
(3) dry: by dry in a vacuum for described composite nano fiber precursor; In this step, dry environment is: vacuum is dry 1 ~ 24h at 0.04 ~ 0.01MPa, temperature 40 ~ 90 DEG C;
(4) calcine: by dried composite nano fiber precursor in an inert atmosphere carbonization become composite nano fiber or nanotube; In this step, dried composite nano fiber precursor calcining heat under inert atmosphere protection is calcined 1 ~ 20h at 400 ~ 1000 DEG C; Described inert gas can be nitrogen, argon gas, hydrogen/argon gas composite gas, hydrogen/nitrogen composite gas;
(5) acid treatment is also dry: the composite nano fiber after carbonization or nanotube acid are processed, and drying obtains described hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber or CNT in a vacuum; In this step, the nanofiber of carbonization or nanotube after calcining are carried out at 20 ~ 80 DEG C of temperature acid treatment with will wherein transition metal dissolution out, wherein acid adopts one or more combinations in nitric acid, sulfuric acid, hydrofluoric acid and hydrochloric acid; Described composite nano fiber or the nanotube dry environment after acid treatment is: vacuum is dry 1 ~ 48h at 0.04 ~ 0.005MPa, temperature 40 ~ 200 DEG C.
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, in described step (1), the described of employing can comprise by cyclisation macromolecule resin: 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 adopted 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 adopted in described step (1) is one or more combinations in water, ethanol, dimethyl formamide, oxolane, acetone and dimethyl sulfoxide (DMSO).
5. according to the preparation method of the hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber/CNT in claim 1-4 described in any one, it is characterized in that, in described step (2), electrospinning parameter is: voltage 9 ~ 25kV, collection distance are 5 ~ 20cm, feeding speed is 0.01 ~ 1mL/h; Wherein the nozzle of electrospinning device is single shaft, coaxial or three coaxial.
6. the hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber obtained according to the preparation method of any one in claim 1-5 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 at 2 ~ 100nm and wherein the thickness of graphitic carbon at 1 ~ 100nm; The diameter of described carbon nano-fiber is at 50 ~ 2000nm, or the diameter of described CNT is at 50 ~ 2500nm, and the pipe diameter of CNT is at 30 ~ 600nm.
7. an electrode, is characterized in that, described electrode is assembled by following material: the hollow plumbago carbon nanometer bead in-situ modification amorphous carbon nanofiber obtained according to the preparation method of any one in claim 1-5 or CNT.
8. lithium ion battery or a ultracapacitor, is characterized in that, has electrode according to claim 7, and the reversible capacity of wherein said lithium ion battery is 400 ~ 1100mAhg
-1; The reversible capacity of described ultracapacitor is 70 ~ 200F/g.
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| CN104600260B (en) * | 2014-12-31 | 2017-01-11 | 江苏锋驰绿色电源有限公司 | C/Ni/S composite material prepared from absorbent cotton and preparation method and application thereof |
| 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 |
| CN106948085B (en) * | 2017-05-08 | 2019-03-05 | 湖北工程学院 | A kind of load has carbon nanofiber membrane of coppe ferrite and preparation method thereof, application |
| CN111321487B (en) * | 2020-04-13 | 2022-10-04 | 青岛大学 | Preparation method of carbon nanofiber with graphene structure on surface |
| CN112174131B (en) * | 2020-10-10 | 2022-08-09 | 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 |
| CN112542564B (en) * | 2020-12-08 | 2021-10-01 | 四川虹微技术有限公司 | Metal lithium cathode with multifunctional bionic membrane constructed in situ and preparation method thereof |
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| CN102021677A (en) * | 2010-10-13 | 2011-04-20 | 清华大学 | Preparation method for carbon nanofiber containing transition metal and nitrogen element and application of carbon nanofiber in fuel-cell catalysts |
| CN102154739A (en) * | 2010-12-30 | 2011-08-17 | 湘潭大学 | Method for preparing lithium ion battery cathode material ZnFe2O4/C nano fibers |
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| CN101874131A (en) * | 2007-11-30 | 2010-10-27 | 丰田自动车株式会社 | Process for production of carbon nanofiber carrying metal microparticles |
| CN102021677A (en) * | 2010-10-13 | 2011-04-20 | 清华大学 | Preparation method for carbon nanofiber containing transition metal and nitrogen element and application of carbon nanofiber in fuel-cell catalysts |
| CN102154739A (en) * | 2010-12-30 | 2011-08-17 | 湘潭大学 | Method for preparing lithium ion battery cathode material ZnFe2O4/C nano fibers |
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