CN108793253A - A kind of one-dimensional transition metal chalcogenide nano wire and its stored energy application - Google Patents

A kind of one-dimensional transition metal chalcogenide nano wire and its stored energy application Download PDF

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CN108793253A
CN108793253A CN201810427115.7A CN201810427115A CN108793253A CN 108793253 A CN108793253 A CN 108793253A CN 201810427115 A CN201810427115 A CN 201810427115A CN 108793253 A CN108793253 A CN 108793253A
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nano wire
metal chalcogenide
transition metal
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phosphorus
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杨雷
张甲甲
代盼盼
陈丽娟
金俊成
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West Anhui University
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    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00Compounds of molybdenum
    • C01G39/06Sulfides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
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    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00Compounds of tungsten
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    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00Compounds of tungsten
    • C01G41/006Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581Chalcogenides or intercalation compounds thereof
    • H01M4/5815Sulfides
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    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/10Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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    • C01INORGANIC CHEMISTRY
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    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/40Electric properties
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention relates to a kind of one-dimensional transition metal chalcogenide nano wire, the one-dimensional transition metal chalcogenide nano wire has the layer structure of similar graphite, and with by MS2Or M2(1‑x)N2xS2The chemical composition of expression, wherein M or N=Mo or W.When one-dimensional nano line produced by the present invention is used as the cathode of lithium ion battery as energy storage material, good embedding lithium, de- lithium performance are shown.

Description

A kind of one-dimensional transition metal chalcogenide nano wire and its stored energy application
Technical field
The present invention relates to technical field of nano material more particularly to a kind of systems of one-dimensional transition metal chalcogenide nano wire The application of Preparation Method and its energy-storage property.
Background technology
In recent years, the hot spot that energy storage material is studied in terms of becoming domestic and international material science and using energy source, energy storage technology can Energy supply and demand unmatched contradiction over time and space is solved, thus is the effective means for improving energy utilization rate.Wherein, lithium Ion battery has that higher than energy, voltage is high, memory-less effect, the excellent characteristics such as has extended cycle life and is widely used in taking down notes (Tarascon etal., Nature, 2001,414,359-367 in this computer, mobile phone and other portable electronic devices; Fergus et al.,Journal of Power Sources,2010,195,939-954).Commercial lithium-ion batteries at present The main graphite stablized using performance has the layer structure of crystallization as negative material, graphite, it is easy to accomplish lithium ion is at it In insertion and deintercalation, and form interlayer compound L iC6.However carbons negative material is because of not high (the 372mA g of its specific capacity H-1) and lithium deposits (Shukla et al., Curri.Sci., 2008,94,314-331;Winter et al., Adv.Mater., 1998,10,725-763) the problems such as prevent it from meeting high-power lithium ion battery, high power capacity, high security Requirement, this so that improving lithium ion battery energy density and safety becomes very poverty-stricken.
Transition metal chalcogenide MoS2、WS2And SnS2Deng due to making lithium ion with the layer structure similar to graphite Can be easily inserted into wherein and deintercalation, thus be also used as lithium ion battery cathode (Du et al., Chem.Commun.,2010,46,1106-1108;Seo et al.,Angew.Chem.,Int.Ed.,2007,46,8828- 8831;Seo et al.,Adv.Mater.,2008,20,4269-4273).Such as based on the Transition Metal Sulfur in nanometer sheet pattern Compound MoS2When cathode of the material as lithium ion battery specific capacity can reach 1131mA h g-1 (Xiao et al., Chem.Mater.,2010,22,4522-4524).Currently, the application for transition metal chalcogenide in lithium ion battery Research is concentrated mainly on block structure and two-dimensional nano chip architecture, and the one-dimentional structure pattern with high-specific surface area is seldom It is reported.
Invention content
Technical problems based on background technology, the present invention are prepared for a large amount of one-dimensional MoS by method of electrostatic spinning2、 WS2And Mo0.5W0.5S2The diameter of nano wire, nano wire is differed at 10 nanometers to 200 nanometers.When they are used as energy storage material When making the cathode of lithium ion battery, excellent storage lithium performance is shown.
A kind of one-dimensional transition metal chalcogenide nano wire, the one-dimensional transition metal chalcogenide nano wire have by MS2Or M2(1-x)N2xS2The chemical composition of expression, wherein M or N=Mo or W.
Preferably, the one-dimensional transition metal chalcogenide nano wire has graphite mould layer structure.
Preferably, a diameter of 10 nanometers to 200 nanometers of the one-dimensional transition metal chalcogenide nano wire, length are 1 μ M to 3mm.
A kind of preparation method of one-dimensional transition metal chalcogenide nano wire, method and step are as follows:
S1:The DMF for measuring certain volume, PVP is dissolved in DMF, then by phosphorus M acid or the mixture of phosphorus M acid and phosphorus N acid It is dissolved in the solution;
S2:The above-mentioned solution being uniformly dissolved is drawn with syringe, by method of electrostatic spinning in suitable operating distance and work Make to prepare phosphorus M acid and PVP or the one-dimensional presoma nano wire of phosphorus M acid and phosphorus N acid compound and PVP composite constructions under voltage;
S3:Spun one-dimensional presoma nano wire is dried to stablize its appearance structure in an oven;
S4:In the environment of inert gas and hydrogen mixed gas, above-mentioned presoma nano wire and S powder are placed on quartz tube type It is heated in stove;
S5:After quartz ampoule cooling, one-dimensional MS is obtained2Or M2(1-x)N2xS2(M or N=Mo or W) nano wire.
Preferably, mass fractions of the PVP in DMF is 1% to 15% in S1, the mixing of phosphorus M acid or phosphorus M acid and phosphorus N acid Mass fraction of the object in DMF is 5% to 40%, and the mass ratio of phosphorus M acid and phosphorus N acid is 0:1 to 1:0.
Preferably, when method of electrostatic spinning prepares presoma nano wire in S2, the electricity between the syringe needle and collecting board of syringe Pressure is 10kV to 25kV, and the distance between syringe needle and collecting board of syringe are 8cm to 20cm.
Preferably, the drying temperature of S3 is 50 DEG C to 150 DEG C.
Preferably, inert gas is nitrogen, helium, neon, argon gas, Krypton and xenon etc., hydrogen and inert gas in S4 Volume ratio be 1:99 to 1:9.
Preferably, in S4, distance is 1cm to 20cm between Sization process presoma nano wire and S powder, and heating temperature is 500 DEG C to 1100 DEG C, heating rate is 2-10 DEG C/min.
A kind of one-dimensional transition metal chalcogenide nano wire proposed by the present invention is in the negative material of lithium ion battery Using.
Compared with prior art, the device have the advantages that being:
The present invention prepares one-dimensional transition metal chalcogenide nano wire using method of electrostatic spinning, the one-dimensional transition metal A diameter of 10 nanometers to 200 nanometers of chalcogenide nano wire, length are 1 μm to 3mm, which has following chemical group At:
One-dimensional transition metal chalcogenide nano wire has by MoS2The chemical composition of expression, when it is used as energy storage material When making the cathode of lithium ion battery, specific capacity maintains 700 mA h g after 100 cycles-1, fluctuation range is 500 mA h g-1To 1000 mA h g-1
One-dimensional transition metal chalcogenide nano wire has by WS2The chemical composition of expression, when it is used as energy storage material When making the cathode of lithium ion battery, specific capacity maintains 400 mA h g after 100 cycles-1, fluctuation range is 300 mA h g-1To 700 mA h g-1
One-dimensional transition metal chalcogenide nano wire has by Mo0.5W0.5S2The chemical composition of expression, when it is as energy storage When material is used as the cathode of lithium ion battery, specific capacity maintains 615 mA h g after 100 cycles-1.Fluctuation range is 400 mA h g-1To 800 mA h g-1
Compared with contrast test, one-dimensional nano line produced by the present invention is more blocky and the transition metal chalcogenide of sheet with Blocky or flake nano material is compared, and has better energy-storage property.
Description of the drawings
Attached drawing is used to provide further understanding of the present invention, and a part for constitution instruction, the reality with the present invention It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the MoS synthesized by embodiment 12SEM figure;
Fig. 2 is the MoS synthesized by embodiment 12XRD spectrum;
Fig. 3 is the MoS synthesized by embodiment 12Cyclic curve figure as lithium ion battery negative material;
Fig. 4 is the WS synthesized by embodiment 22SEM figure;
Fig. 5 is the WS synthesized by embodiment 22XRD spectrum;
Fig. 6 is the WS synthesized by embodiment 22Cyclic curve figure as lithium ion battery negative material;
Fig. 7 is the Mo synthesized by embodiment 30.5W0.5S2SEM figure;
Fig. 8 is the Mo synthesized by embodiment 30.5W0.5S2TEM figure;
Fig. 9 is the Mo synthesized by embodiment 30.5W0.5S2Cyclic curve figure as lithium ion battery negative material.
Specific implementation mode
The present invention is made further to explain with reference to specific embodiment.
Embodiment 1
One-dimensional transition metal chalcogenide nano wire MoS2Preparation, characterization and energy-storage property
(1) 5 mL DMF are measured with graduated cylinder, 0.5 g PVP is weighed with assay balance, in the stirring action of magnetic stirring apparatus Under, PVP is slowly added into DMF, after abundant dissolving, 1g phosphomolybdic acids are added in above-mentioned solution, be sufficiently stirred until Solution colour is uniform;
(2) above-mentioned solution is drawn with syringe, by method of electrostatic spinning in the operating distance of 15cm and the work of 16kV Under voltage, the one-dimensional presoma nano wire of phosphomolybdic acid and PVP composite constructions is prepared;
(3) above-mentioned presoma nano wire is transferred in the baking oven that temperature is 80 DEG C and is dried to stablize its appearance structure;
(4) two ceramic boats are placed in the quartz ampoule of tube furnace, wherein the ceramic boat for holding nanowire precursor is placed on The center of quartz ampoule, the ceramic boat for holding S powder are placed on the upstream of nanowire precursor, and it is 10cm to keep the distance of the two.
(5) after closed good quartz ampoule, the inner air of quartz ampoule is arranged with vacuum pump and argon hydrogen gaseous mixture (5% hydrogen) To the greatest extent, and make to be argon hydrogen gaseous mixture (5% hydrogen) environment in pipe.
(6) quartz ampoule is heated to 900 DEG C from room temperature with the heating rate of 5 DEG C/min, keeps the temperature 1 hour at 925 DEG C, then Entire stove is allowed to naturally cool to room temperature.Whole experiment process keep argon hydrogen gaseous mixture (5% hydrogen) air-flow size be 50sccm。
(7) after dropping to room temperature, the presoma nano wire in the ceramic boat in quartz ampoule center is transformed into MoS2Nano wire.With sweeping Electron microscope observation its pattern is retouched, as shown in Fig. 1, nanowire diameter is differed at 10 nanometers to 200 nanometers;X in attached drawing 2 Ray diffraction spectra shows that synthesized nano wire is pure phase MoS2Nano wire.
Performance test:By MoS2As the negative material of 2032 button cells, the specific manufacturing process of battery is as follows:With 80 : 10: 10 mass ratio, by active material, Super P and Kynoar (PVDF) mixed grinding, wherein activity substance content About 5 milligrams, suitable N-Methyl pyrrolidone solution (NMP) is added dropwise after grinding again, stirs evenly, is coated on copper foil, first 80 DEG C of common drying 6h, rolling are sliced into the pole piece of a diameter of 14mm, the vacuum drying at 120 DEG C in vacuum drying chamber 12h.Using metal lithium sheet as to electrode,2325 be diaphragm, the LiPF of 1mol/L6Solution (wherein electrolyte solvent For the mixed solvent (mass ratio of EC and DEC are 1: 1) of ethylene carbonate (EC) and diethyl carbonate (DEC)) it is electrolyte.? Glove box (O full of high-purity argon gas2 and H2O<Button cell is assembled into 1ppm).Fig. 3 gives it as lithium-ion electric Cycle performance of the pond negative material under 100mA/g current densities, after 100 cycles, specific capacity maintains 700 mA h g-1
Embodiment 2
One-dimensional transition metal chalcogenide nano wire WS2Preparation, characterization and energy-storage property
(1) 5 mL DMF are measured with graduated cylinder, 0.5 g PVP is weighed with assay balance, in the stirring action of magnetic stirring apparatus Under, PVP is slowly added into DMF, after abundant dissolving, 1g phosphotungstic acids are added in above-mentioned solution, be sufficiently stirred until Solution colour is uniform;
(2) above-mentioned solution is drawn with syringe, by method of electrostatic spinning in the operating distance of 15cm and the work of 16kV Under voltage, the one-dimensional presoma nano wire of phosphotungstic acid and PVP composite constructions is prepared;
(3) above-mentioned presoma nano wire is transferred in the baking oven that temperature is 80 DEG C and is dried to stablize its appearance structure;
(4) two ceramic boats are placed in the quartz ampoule of tube furnace, wherein the ceramic boat for holding nanowire precursor is placed on The center of quartz ampoule, the ceramic boat for holding S powder are placed on the upstream of nanowire precursor, and it is 10cm to keep the distance of the two.
(5) after closed good quartz ampoule, the inner air of quartz ampoule is arranged with vacuum pump and argon hydrogen gaseous mixture (5% hydrogen) To the greatest extent, and make to be argon hydrogen gaseous mixture (5% hydrogen) environment in pipe.
(6) quartz ampoule is heated to 900 DEG C from room temperature with the heating rate of 5 DEG C/min, keeps the temperature 1 hour at 925 DEG C, then Entire stove is allowed to naturally cool to room temperature.Whole experiment process keep argon hydrogen gaseous mixture (5% hydrogen) air-flow size be 50sccm。
(7) after dropping to room temperature, the presoma nano wire in the ceramic boat in quartz ampoule center is transformed into WS2 nano wires.With sweeping Electron microscope observation its pattern is retouched, as shown in Fig. 4, nanowire diameter is differed at 10 nanometers to 200 nanometers;X in attached drawing 5 Ray diffraction spectra shows that synthesized nano wire is pure phase WS2 nano wires.
Performance test:At room temperature, by WS2As the negative material of 2032 button cells, the specific manufacturing process of battery It is as follows:With 80: 10: 10 mass ratio, by active material, Super P and Kynoar (PVDF) mixed grinding, wherein activity Content of material is about 5 milligrams, and suitable N-Methyl pyrrolidone solution (NMP) is added dropwise after grinding again, stirs evenly, is coated to copper On foil, prior to 80 DEG C in vacuum drying chamber common drying 6h, rolling is sliced into the pole piece of a diameter of 14mm, true at 120 DEG C Sky drying 12h.Using metal lithium sheet as to electrode,2325 be diaphragm, and the LiPF6 solution of 1mol/L (is wherein electrolysed Liquid solvent is the mixed solvent (mass ratio of EC and DEC are 1: 1) of ethylene carbonate (EC) and diethyl carbonate (DEC)) it is electricity Solve liquid.In glove box (the O2 and H2O full of high-purity argon gas<Button cell is assembled into 1ppm).Fig. 6 gives its conduct Cycle performance of the lithium ion battery negative material under 100 mA/g current densities, after 100 cycles, specific capacity maintains In 400 mA h g-1
Embodiment 3
One-dimensional transition metal chalcogenide nano wire Mo0.5W0.5S2Preparation, characterization and energy-storage property
(1) 5 mL DMF are measured with graduated cylinder, 0.5 g PVP is weighed with assay balance, in the stirring action of magnetic stirring apparatus Under, PVP is slowly added into DMF, after abundant dissolving, 0.5g phosphomolybdic acids and 0.5g phosphotungstic acids are added to above-mentioned solution In, it is sufficiently stirred until solution colour is uniform;
(2) above-mentioned solution is drawn with syringe, by method of electrostatic spinning in the operating distance of 15cm and the work of 16kV Under voltage, the one-dimensional presoma nano wire of phosphomolybdic acid, phosphotungstic acid and PVP composite constructions is prepared;
(3) above-mentioned presoma nano wire is transferred in the baking oven that temperature is 80 DEG C and is dried to stablize its appearance structure;
(4) two ceramic boats are placed in the quartz ampoule of tube furnace, wherein the ceramic boat for holding nanowire precursor is placed on The center of quartz ampoule, the ceramic boat for holding S powder are placed on the upstream of nanowire precursor, and it is 10cm to keep the distance of the two.
(5) after closed good quartz ampoule, the inner air of quartz ampoule is arranged with vacuum pump and argon hydrogen gaseous mixture (5% hydrogen) To the greatest extent, and make to be argon hydrogen gaseous mixture (5% hydrogen) environment in pipe.
(6) quartz ampoule is heated to 900 DEG C from room temperature with the heating rate of 5 DEG C/min, keeps the temperature 1 hour at 925 DEG C, then Entire stove is allowed to naturally cool to room temperature.Whole experiment process keep argon hydrogen gaseous mixture (5% hydrogen) air-flow size be 50sccm。
(7) after dropping to room temperature, the presoma nano wire in the ceramic boat in quartz ampoule center is transformed into Mo0.5W0.5S2 nanometers Line.Its pattern is observed with scanning electron microscope, as shown in Fig. 7, nanowire diameter is differed at 10 nanometers to 200 nanometers;It is attached Fig. 8 illustrates transmission electron micrograph, it can be seen that synthesized nano wire be accumulated by many nano particles and At.
Performance test:At room temperature, by Mo0.5W0.5S2As the negative material of 2032 button cells, the specific system of battery It is as follows to make process:With 80: 10: 10 mass ratio, by active material, Super P and Kynoar (PVDF) mixed grinding, Middle activity substance content is about 5 milligrams, and suitable N-Methyl pyrrolidone solution (NMP) is added dropwise after grinding again, stirs evenly, and is applied It is layed onto on copper foil, prior to 80 DEG C in vacuum drying chamber common drying 6h, rolling is sliced into the pole piece of a diameter of 14mm, then at 120 Vacuum drying 12h at DEG C.Using metal lithium sheet as to electrode,2325 be diaphragm, LiPF6 solution (its of 1mol/L Middle electrolyte solvent be ethylene carbonate (EC) and diethyl carbonate (DEC) mixed solvent (mass ratio of EC and DEC are 1: 1)) it is electrolyte.In glove box (the O2 and H2O full of high-purity argon gas<Button cell is assembled into 1ppm).Fig. 9 gives Its cycle performance as lithium ion battery negative material under 100 mA/g current densities, after 100 cycles, specific volume Amount maintains 615 mA h g-1
Embodiment 4
A kind of preparation method of one-dimensional transition metal chalcogenide nano wire, method and step are as follows:
(1) 5 mL DMF are measured with graduated cylinder, 0.05 g PVP is weighed with assay balance, in the stirring action of magnetic stirring apparatus Under, PVP is slowly added into DMF, after abundant dissolving, 0.5g phosphomolybdic acids are added in above-mentioned solution, is sufficiently stirred straight It is uniform to solution colour;
(2) above-mentioned solution is drawn with syringe, by method of electrostatic spinning in the operating distance of 8cm and the work of 10 kV Under voltage, the one-dimensional presoma nano wire of phosphomolybdic acid and PVP composite constructions is prepared;
(3) above-mentioned presoma nano wire is transferred in the baking oven that temperature is 50 DEG C and is dried to stablize its appearance structure;
(4) two ceramic boats are placed in the quartz ampoule of tube furnace, wherein the ceramic boat for holding nanowire precursor is placed on The center of quartz ampoule, the ceramic boat for holding S powder are placed on the upstream of nanowire precursor, and it is 1cm to keep the distance of the two.
(5) after closed good quartz ampoule, the inner air of quartz ampoule is arranged with vacuum pump and nitrogen and hydrogen mixture (1% hydrogen) To the greatest extent, and make to be nitrogen and hydrogen mixture (1% hydrogen) environment in pipe.
(6) quartz ampoule is heated to 500 DEG C from room temperature with the heating rate of 2 DEG C/min, keeps the temperature 1 hour at 500 DEG C, then Entire stove is allowed to naturally cool to room temperature.Whole experiment process keep nitrogen and hydrogen mixture (1% hydrogen) air-flow size be 50sccm。
(7) after dropping to room temperature, the presoma nano wire in the ceramic boat in quartz ampoule center is transformed into MoS2Nano wire.
Embodiment 5
A kind of one-dimensional WS2The preparation method of nano wire, method and step are as follows:
(1) 5 mL DMF are measured with graduated cylinder, 0.75 g PVP is weighed with assay balance, in the stirring action of magnetic stirring apparatus Under, PVP is slowly added into DMF, after abundant dissolving, 2g phosphotungstic acids are added in above-mentioned solution, be sufficiently stirred until Solution colour is uniform;
(2) above-mentioned solution is drawn with syringe, by method of electrostatic spinning in the operating distance of 20cm and the work of 25 kV Under voltage, the one-dimensional presoma nano wire of phosphotungstic acid and PVP composite constructions is prepared;
(3) above-mentioned presoma nano wire is transferred in the baking oven that temperature is 150 DEG C and is dried to stablize its appearance structure;
(4) two ceramic boats are placed in the quartz ampoule of tube furnace, wherein the ceramic boat for holding nanowire precursor is placed on The center of quartz ampoule, the ceramic boat for holding S powder are placed on the upstream of nanowire precursor, and it is 20cm to keep the distance of the two.
(5) after closed good quartz ampoule, the inner air of quartz ampoule is arranged with vacuum pump and argon hydrogen gaseous mixture (10% hydrogen) To the greatest extent, and make to be argon hydrogen gaseous mixture (10% hydrogen) environment in pipe.
(6) quartz ampoule is heated to 1100 DEG C from room temperature with the heating rate of 10 DEG C/min, 1 hour is kept the temperature at 1100 DEG C, Then entire stove is allowed to naturally cool to room temperature.Whole experiment process keep argon hydrogen gaseous mixture (10% hydrogen) air-flow size be 50sccm。
(7) after dropping to room temperature, the presoma nano wire in the ceramic boat in quartz ampoule center is transformed into WS2Nano wire.
Contrast test
With reference to the performance test method of embodiment, using blocky and two-dimensional nano piece WS2As the negative of 2032 button cells Pole material tests its performance under 100mA/g current densities, after 100 cycles, the WS of block structure2Specific capacity dimension It holds in 320 mA h g-1, fluctuation range is 220 mA h g-1To 400 mA h g-1;The WS of laminated structure2Specific capacity maintain In 350 mA h g-1, fluctuation range is 290 mA h g-1To 380 mA h g-1
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.

Claims (10)

1. a kind of one-dimensional transition metal chalcogenide nano wire, which is characterized in that the one-dimensional transition metal chalcogenide nanometer Line has by MS2Or M2(1-x)N2xS2The chemical composition of expression, wherein M or N=Mo or W.
2. a kind of one-dimensional transition metal chalcogenide nano wire according to claim 1, which is characterized in that the one-dimensional mistake Crossing metal chalcogenide nano wire has graphite mould layer structure.
3. a kind of one-dimensional transition metal chalcogenide nano wire according to claim 1, which is characterized in that the one-dimensional mistake Cross metal chalcogenide nano wire a diameter of 10 nanometers to 200 nanometers, length are 1 μm to 3mm.
4. a kind of preparation method of one-dimensional transition metal chalcogenide nano wire according to claim 1, which is characterized in that Method and step is as follows:
S1:The DMF for measuring certain volume, PVP is dissolved in DMF, then phosphorus M acid or phosphorus M acid and the mixture of phosphorus N acid are dissolved In the solution;
S2:The above-mentioned solution being uniformly dissolved is drawn with syringe, by method of electrostatic spinning in suitable operating distance and work electricity Phosphorus M acid and PVP or the one-dimensional presoma nano wire of phosphorus M acid and phosphorus N acid compound and PVP composite constructions are prepared in pressure;
S3:Spun one-dimensional presoma nano wire is dried to stablize its appearance structure in an oven;
S4:In the environment of inert gas and hydrogen mixed gas, above-mentioned presoma nano wire and S powder are placed in quartz tube furnace Heating;
S5:After quartz ampoule cooling, one-dimensional MS is obtained2Or M2(1-x)N2xS2(M or N=Mo or W) nano wire.
5. a kind of preparation method of one-dimensional transition metal chalcogenide nano wire according to claim 4, which is characterized in that Mass fractions of the PVP in DMF is 1% to 15% in S1, the quality of phosphorus M acid or the mixture of phosphorus M acid and phosphorus N acid in DMF Score is 5% to 40%, and the mass ratio of phosphorus M acid and phosphorus N acid is 0:1 to 1:0.
6. a kind of preparation method of one-dimensional transition metal chalcogenide nano wire according to claim 4, which is characterized in that When method of electrostatic spinning prepares presoma nano wire in S2, the voltage between the syringe needle and collecting board of syringe is 10kV to 25kV, The distance between syringe needle and collecting board of syringe are 8cm to 20cm.
7. a kind of preparation method of one-dimensional transition metal chalcogenide nano wire according to claim 4, which is characterized in that The drying temperature of S3 is 50 DEG C to 150 DEG C.
8. a kind of preparation method of one-dimensional transition metal chalcogenide nano wire according to claim 4, which is characterized in that Inert gas is nitrogen, helium, neon, argon gas, Krypton and xenon etc. in S4, and the volume ratio of hydrogen and inert gas is 1:99 to 1:9。
9. a kind of preparation method of one-dimensional transition metal chalcogenide nano wire according to claim 4, which is characterized in that In S4, distance is 1cm to 20cm between Sization process presoma nano wire and S powder, and heating temperature is at 500 DEG C to 1100 DEG C, heating Rate is 2-10 DEG C/min.
10. a kind of one-dimensional transition metal chalcogenide nano wire of claim 1-3 any one of them is in the negative of lithium ion battery Application in the material of pole.
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