CN102605468A - Method for preparing nickel sulfide nano-fibers - Google Patents

Abstract

The invention relates to a method for preparing nickel sulfide nanofibers, belonging to the technical field of nanomaterial preparation. The invention adopts the combination of electrospinning technology and vulcanization technology to prepare NiS nanofibers. The present invention comprises three steps: (1) preparing spinning solution. Adding Ni(NO ₃ ) ₂ ·6H ₂ O and PVP into DMF solvent to form a spinning solution; (2) preparing NiO nanofibers. The PVP/Ni(NO ₃ ) ₂ composite nanofibers were prepared by electrospinning technology, and then NiO nanofibers were obtained by heat treatment; (3) NiS nanofibers were prepared. NiO nanofibers were vulcanized by CS ₂ to obtain NiS nanofibers with a novel structure and pure phase, which had a good crystal form, a diameter of 45-80nm, and a length of more than 50μm. NiS nanofiber is an important functional material, which will be applied in photocatalysis, infrared detection, solar energy storage, photosensitive materials and other fields. The preparation method of the invention is simple and easy, can be produced in batches, and has broad application prospects.

Description

A kind of method for preparing the nanometer nickel sulfide fiber

Technical field

The present invention relates to the nano material preparation technical field, relate to a kind of method for preparing the nanometer nickel sulfide fiber specifically.

Background technology

Nanofiber is meant the filamentary material that on the three dimensions yardstick of material, has bidimensional to be in nanoscale, and radial dimension is a nanometer scale usually, and length is then bigger.Because the radial dimension of nanofiber is little of nanometer scale; Demonstrate series of characteristics; The most outstanding is that specific area is big; Thereby its surface energy increases with active, and then produces small-size effect, surface or interfacial effect, quantum size effect, macro quanta tunnel effect etc., and therefore shows the specificity of a series of chemistry, physics (heat, light, sound, electricity, magnetic etc.) aspect.In the prior art, a lot of methods that prepare nanofiber are arranged, the method for for example reeling off raw silk from cocoons, template synthetic method, split-phase method and self-assembly method etc.In addition, also has arc evaporation, laser high temperature inustion, compound pyrolysismethod.These three kinds of methods in fact all are after at high temperature making compound (or simple substance) evaporation, make nanofiber or nanotube through pyrolysis (or directly condensation), from essence, all belong to the compound steam sedimentation.

Nickel sulfide NiS is a kind of important functional material, is widely used in fields such as photocatalysis, infrared acquisition, solar energy storage, light-sensitive material.At present, adopted hydro-thermal method, solvent-thermal method etc. to prepare nano materials such as nickel sulfide monocrystal nano rod, nanosphere, nano belt, nano particle, sea urchin shape nanostructured, layering carnation structure, flower-like nanostructure.The nanometer nickel sulfide fiber is a kind of important new function material, will have important application prospects.Do not see at present that adopting electrostatic spinning technique to combine with sulfurization technology prepares the report of NiS nanofiber.

The patent No. is the technical scheme that 1975504 United States Patent (USP) discloses a relevant electrospinning process (electrospinning); This method is a kind of effective ways that prepare continuous, as to have macro length micro nanometer fiber, is at first proposed in 1934 by Formhals.This method mainly is used for preparing high polymer nanometer fiber; It is characterized in that making charged Polymer Solution or melt in electrostatic field, to receive the traction of electrostatic force and spray, invest the receiving screen on opposite, thereby realize wire drawing by nozzle; Then; Solvent evaporation at normal temperatures, perhaps melt is cooled to normal temperature and solidifies, and obtains micro nanometer fiber.Over nearly 10 years, occurred adopting electrospinning process to prepare the technical scheme of inorganic compound such as oxidate nano fiber at the inorfil preparing technical field, described oxide comprises TiO ₂, ZrO ₂, Y ₂O ₃, Y ₂O ₃: RE ³⁺(RE ³⁺=Eu ³⁺, Tb ³⁺, Er ³⁺, Yb ³⁺/ Er ³⁺), NiO, Co ₃O ₄, Mn ₂O ₃, Mn ₃O ₄, CuO, SiO ₂, Al ₂O ₃, V ₂O ₅, ZnO, Nb ₂O ₅, MoO ₃, CeO ₂, LaMO ₃(M=Fe, Cr, Mn, Co, Ni, Al), Y ₃Al ₅O ₁₂, La ₂Zr ₂O ₇Deng metal oxide and composite oxide of metal.Employing electrostatic spinning techniques such as Wang Jinxian have prepared rare earth fluoride/rare earth oxyfluoride composite nano fibre (Chinese invention patent, application number: 200810050959.0).Electrospinning process can prepare big L/D ratio micrometer fibers or nanofiber continuously.At present, do not see that adopting electrostatic spinning technique to combine with sulfurization technology prepares the report of NiS nanofiber.

When utilizing electrostatic spinning technique to prepare nano material, the composition of the kind of raw material, the molecular weight of high polymer templates, spinning solution, spinning process parameter and Technology for Heating Processing all have material impact to the pattern and the size of final products.The present invention adopts electrostatic spinning technique earlier, with Nickelous nitrate hexahydrate Ni (NO ₃) ₂6H ₂O is a raw material, adds solvent N, and dinethylformamide DMF and high polymer templates polyvinylpyrrolidone PVP obtain carrying out electrostatic spinning behind the spinning solution, under the experiment condition of the best, prepare PVP/Ni (NO ₃) ₂Original nanofiber is heat-treated it in air, obtain nickel oxide NiO nanofiber, again with carbon disulfide CS ₂For vulcanizing agent vulcanizes, prepared the NiS nanofiber of the pure phase of novel structure.

Summary of the invention

Various in background technology prepare in the method for nanofiber, the shortcoming of the method for reeling off raw silk from cocoons be solution viscosity is required too harsh; The shortcoming of template synthetic method is to prepare the continuous fibers that the root root separates; Split-phase method and self-assembly method production efficiency are all lower; And the compound steam sedimentation is because to the demand of high temperature, so process conditions are difficult to control, and the nanofiber major diameter of above-mentioned several method preparation is than little.Use electrostatic spinning technique in the background technology has prepared metal oxide, composite oxide of metal nanofiber and rare earth fluoride/rare earth oxyfluoride composite nano fibre.Prior art adopts hydro-thermal method, solvent-thermal method etc. to prepare nano materials such as nickel sulfide monocrystal nano rod, nanosphere, nano belt, nano particle, sea urchin shape nanostructured, layering carnation structure, flower-like nanostructure.In order to provide the NiS nanofiber a kind of new preparation method, we combine electrostatic spinning technique with sulfurization technology, invented a kind of preparation method of NiS nanofiber.

The present invention is achieved in that and at first prepares the spinning solution with certain viscosity that is used for electrostatic spinning, uses electrostatic spinning technique and carries out electrostatic spinning, under the experiment condition of the best, prepares PVP/Ni (NO ₃) ₂Original nanofiber is heat-treated it in air, obtain the NiO nanofiber, again with carbon disulfide CS ₂For vulcanizing agent vulcanizes, prepared the NiS nanofiber of the pure phase of novel structure.The steps include:

(1) preparing spinning solution

That use in the nickel source is Nickelous nitrate hexahydrate Ni (NO ₃) ₂6H ₂O, high polymer templates adopts polyvinylpyrrolidone PVP, and molecular weight is 1300000, adopts N, and dinethylformamide DMF is a solvent, takes by weighing a certain amount of Ni (NO ₃) ₂6H ₂O and PVP join in an amount of DMF solvent, stir 6h in the room temperature lower magnetic force, and leave standstill 4h, promptly form spinning solution, and the mass percent of this each part of spinning solution is: nickel nitrate content 8%, PVP content 14%, solvent DMF content 78%;

(2) preparation NiO nanofiber

The spinning solution for preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, shower nozzle internal diameter 1mm; The angle of adjustment shower nozzle and horizontal plane is 30 °, applies the DC voltage of 15kV, solidifies apart from 18cm; 18～25 ℃ of room temperatures, relative humidity is 50%～65%, obtains PVP/Ni (NO ₃) ₂Composite nano fiber is with described PVP/Ni (NO ₃) ₂Composite nano fiber is put in the temperature programmed control stove and heat-treats, and heating rate is 1 ℃/min, and at 600 ℃ of constant temperature 4h, the speed with 1 ℃/min is cooled to 200 ℃ again, naturally cools to room temperature with body of heater afterwards, obtains the NiO nanofiber;

(3) preparation NiS nanofiber

Sulfuration reagent uses carbon disulfide CS ₂, described NiO nanofiber is put into the corundum Noah's ark, Noah's ark places in the vacuum tube furnace, when room temperature, feeds argon Ar 30min, discharges the air in the boiler tube, feeds CS when being warming up to 700 ℃ with the rate of heat addition of 5 ℃/min ₂Gas, insulation 1h reduces to 200 ℃ with the rate of temperature fall of 5 ℃/min again, naturally cools to room temperature afterwards, obtains the NiS nanofiber, and diameter is 45～80nm, and length is greater than 50 μ m.

NiS nanofiber described in the said process has good crystal formation, and diameter is 45～80nm, and length has realized goal of the invention greater than 50 μ m.

Description of drawings

Fig. 1 is the XRD spectra of NiS nanofiber;

Fig. 2 is the SEM photo of NiS nanofiber, this figure double as Figure of abstract;

Fig. 3 is the EDS spectrogram of NiS nanofiber;

Fig. 4 is the dielectric constant figure of NiS nanofiber;

Fig. 5 is the dielectric loss figure of NiS nanofiber;

Fig. 6 is the conductivity map of NiS nanofiber.

The specific embodiment

Nickelous nitrate hexahydrate Ni (the NO that the present invention selected for use ₃) ₂6H ₂O, polyvinylpyrrolidone PVP, molecular weight 1300000, N, dinethylformamide DMF, carbon disulfide CS ₂, be commercially available analysis net product; Used glass apparatus, crucible and equipment are instrument and equipments commonly used in the laboratory.

Embodiment: take by weighing a certain amount of Ni (NO ₃) ₂6H ₂O and PVP join in an amount of DMF solvent, stir 6h in the room temperature lower magnetic force, and leave standstill 4h, promptly form spinning solution, and the mass percent of this each part of spinning solution is: nickel nitrate content 8%, PVP content 14%, solvent DMF content 78%; The spinning solution for preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, shower nozzle internal diameter 1mm; The angle of adjustment shower nozzle and horizontal plane is 30 °, applies the DC voltage of 15kV, solidifies apart from 18cm; 18～25 ℃ of room temperatures, relative humidity is 50%～65%, obtains PVP/Ni (NO ₃) ₂Composite nano fiber is with described PVP/Ni (NO ₃) ₂Composite nano fiber is put in the temperature programmed control stove and heat-treats, and heating rate is 1 ℃/min, and at 600 ℃ of constant temperature 4h, the speed with 1 ℃/min is cooled to 200 ℃ again, naturally cools to room temperature with body of heater afterwards, obtains the NiO nanofiber; Sulfuration reagent uses carbon disulfide CS ₂, described NiO nanofiber is put into the corundum Noah's ark, Noah's ark places in the vacuum tube furnace, when room temperature, feeds argon Ar 30min, discharges the air in the boiler tube, feeds CS when being warming up to 700 ℃ with the rate of heat addition of 5 ℃/min ₂Gas, insulation 1h reduces to 200 ℃ with the rate of temperature fall of 5 ℃/min again, naturally cools to room temperature afterwards, obtains the NiS nanofiber.Described NiS nanofiber has good crystallinity, and listed d value and the relative intensity of the d value of its diffraction maximum and relative intensity and the PDF standard card (65-3419) of NiS is consistent, belongs to hexagonal crystal system, and space group is P63/mmc, sees shown in Figure 1.The diameter of described NiS nanofiber is 45～80nm, and length is seen shown in Figure 2 greater than 50 μ m.The NiS nanofiber is formed (the Au conductive layer of surface plating when Au derives from the SEM sample preparation) by Ni and S element, sees shown in Figure 3.The dielectric constant of NiS nanofiber does not almost change with the increase of ac frequency, sees shown in Figure 4.The dielectric loss of NiS nanofiber reduces with the increase of ac frequency, sees shown in Figure 5.The electrical conductivity of NiS nanofiber reduces with the increase of ac frequency, sees shown in Figure 6.

Certainly; The present invention also can have other various embodiments; Under the situation that does not deviate from spirit of the present invention and essence thereof; Those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.

Claims (2)

1. a method for preparing the nanometer nickel sulfide fiber is characterized in that, the method that adopts electrostatic spinning technique to combine with sulfurization technology; Polyvinylpyrrolidone PVP is a high polymer templates; Adopt N, dinethylformamide DMF is a solvent, and sulfuration reagent uses carbon disulfide CS ₂, the preparation product is a nickel sulfide NiS nanofiber, the steps include:

(1) preparing spinning solution

Take by weighing a certain amount of Nickelous nitrate hexahydrate Ni (NO ₃) ₂6H ₂O and PVP join in an amount of DMF solvent, stir 6h in the room temperature lower magnetic force, and leave standstill 4h, promptly form spinning solution, and the mass percent of this each part of spinning solution is: nickel nitrate content 8%, PVP content 14%, solvent DMF content 78%;

(2) preparation NiO nanofiber

The spinning solution for preparing is added in the liquid storage pipe of device for spinning, carry out electrostatic spinning, shower nozzle internal diameter 1mm; The angle of adjustment shower nozzle and horizontal plane is 30 °, applies the DC voltage of 15kV, solidifies apart from 18cm; 18～25 ℃ of room temperatures, relative humidity is 50%～65%, obtains PVP/Ni (NO ₃) ₂Composite nano fiber is with described PVP/Ni (NO ₃) ₂Composite nano fiber is put in the temperature programmed control stove and heat-treats, and heating rate is 1 ℃/min, and at 600 ℃ of constant temperature 4h, the speed with 1 ℃/min is cooled to 200 ℃ again, naturally cools to room temperature with body of heater afterwards, obtains the NiO nanofiber;

(3) preparation NiS nanofiber

Sulfuration reagent uses carbon disulfide CS ₂, described NiO nanofiber is put into the corundum Noah's ark, Noah's ark places in the vacuum tube furnace, when room temperature, feeds argon Ar 30min, discharges the air in the boiler tube, feeds CS when being warming up to 700 ℃ with the rate of heat addition of 5 ℃/min ₂Gas, insulation 1h reduces to 200 ℃ with the rate of temperature fall of 5 ℃/min again, naturally cools to room temperature afterwards, obtains the NiS nanofiber, and diameter is 45～80nm, and length is greater than 50 μ m.

2. a kind of method for preparing the nanometer nickel sulfide fiber according to claim 1 is characterized in that high polymer templates is the polyvinylpyrrolidone of molecular weight Mr=1300000.

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