CN103762356A - Ni nanowire, NiO/Ni self-support membrane and preparation method and application thereof - Google Patents

Ni nanowire, NiO/Ni self-support membrane and preparation method and application thereof Download PDF

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CN103762356A
CN103762356A CN201310740240.0A CN201310740240A CN103762356A CN 103762356 A CN103762356 A CN 103762356A CN 201310740240 A CN201310740240 A CN 201310740240A CN 103762356 A CN103762356 A CN 103762356A
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nano wire
self
nio
supported membrane
solution
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CN103762356B (en
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高义华
刘逆霜
马文真
李建
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Huazhong University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • 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

Abstract

The invention discloses a Ni nanowire, a NiO/Ni self-support membrane and a preparation method and application thereof. The Ni nanowire is a super-long nanowire with average length of 50,000-200,000nm. The preparation method of the Ni nanowire comprises the steps of firstly preparing liquid-phase growth liquid for the Ni nanowire; then preparing the elementary substance of the Ni nanowire in an applied magnetic field; finally separating and purifying the Ni nanowire. The NiO/Ni self-support membrane comprises the Ni nanowire and a Ni nanowire obtained by calcining the Ni nanowire and having NiO on the surface. The preparation method of the NiO/Ni self-support membrane comprises the steps of firstly dispersing the Ni nanowire in a surfactant solution; then performing suction filtration and transferring the Ni nanowire onto a microfiltration membrane to obtain a Ni self-support membrane; finally, calcining the Ni self-support membrane in an oxygen-containing atmosphere to obtain the NiO/Ni self-support membrane. The NiO/Ni self-support membrane disclosed by the invention has good flexibility and electrochemical properties and can be used as a super-capacitor active material, the cost is low, and the process is simple.

Description

Ni nano wire, NiO/Ni self-supported membrane and its preparation method and application
Technical field
The invention belongs to field of nanometer material technology, more specifically, relate to a kind of Ni nano wire, NiO/Ni self-supported membrane and its preparation method and application.
Background technology
Along with the approach exhaustion gradually of traditional fossil energy, there are the new forms of energy of the advantages such as environmental protection, recyclability as solar energy, wind energy, nuclear energy, geothermal energy etc. have received the increasing concern of people and developed, application, and new forms of energy often exist the problem of an electrical power storage in the process of generating electricity by way of merging two or more grid systems, and perhaps the advantage of ultracapacitor aspect stored energy can well address these problems.
The people such as Yuan have delivered one piece with MnO at nature nanotechnology in 2008 2self-supported membrane is basis, then by de-agglomerate dimethyl siloxane (PDMS) at absorption at 234 ℃ and 390 ℃, reaches the object of hydrophobic/hydrophilic, has huge application potential adsorbing aspect greasy dirt.The people such as Luo have obtained CNT/LiCoO in 2012 by the method for simply overlength, super neat carbon nano-tube and lithium cobalt oxygen micron particles being carried out to ultrasonic codeposition 2the self-supported membrane that composite material forms, be different from conventional lithium ion cell positive and need to add extra conductive agent (as conductive carbon black, acetylene black etc.), this preparation method both provided cost savings, be conducive to the simplification of preparation section simultaneously, this self-supported membrane is under 0.1C, and specific capacity reaches 151.4mAhg -1, show good performance of lithium ion battery.The people such as Yuan take graphene oxide/carbon nano-tube film as substrate, then went out ultracapacitor active material Co by hydro-thermal reaction direct growth on composite material of 14 hours at 90 ℃ in 2012 3o 4, at 2Ag -1charging and discharging currents density under obtained 378Fg -1ratio electric capacity, there is fabulous pliability simultaneously.
Metal oxide based capacitor research at present the most successfully electrode material is mainly ruthenium-oxide, but due to the resource-constrained of noble metal, selling at exorbitant prices has limited the use to it, is mainly to reduce the cost of material for the research of metal oxide capacitor, finds more cheap material.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides a kind of Ni nano wire, NiO/Ni self-supported membrane and its preparation method and application, its object is to provide that a kind of pliability is good, charge-discharge performance is good and lower-cost super capacitor electrode active material, solves thus that current super capacitor cost is high, the technical problem of complex manufacturing technology.
For achieving the above object, according to one aspect of the present invention, provide a kind of Ni nano wire, described Ni nano wire average diameter is between 200nm to 300nm, and average length is 50, and 000nm to 200, between 000nm.
According to another aspect of the present invention, a kind of preparation method of Ni nano wire is provided, comprise the following steps:
(1) configuration Ni nano wire liquid growth liquid: using Ni salt as presoma, be dissolved in organic solvent, make Ni precursor solution; Organic reducing agent is dissolved in described organic solvent, makes reductant solution; Ni precursor solution is slowly scattered in strong basicity organic solvent, then adds reductant solution, finally add surfactant organic solution, make Ni nano wire liquid growth liquid;
(2), under externally-applied magnetic field, make Ni nano wire liquid growth liquid generation redox reaction, preparation Ni nano wire simple substance;
(3) Magnetic Isolation clean Ni nano wire simple substance, makes Ni nano wire as claimed in claim 1 after dry.
Preferably, described preparation method, the described Ni salt of its step (1) is Nickel dichloride hexahydrate, and described organic solvent is ethylene glycol, and described Ni precursor solution concentration is 24mg/ml; Described organic reducing agent is hydrazine hydrate, and described organic reducing agent solution concentration is 85wt%; The NaOH ethylene glycol solution that described strong basicity organic solvent is 1.5mol/L; The polyvinylpyrrolidone that described surfactant organic solution is 2wt%; The mixed proportion of described Ni precursor solution, strong basicity organic solution, reducing agent organic solution is volume ratio 1:4:2.
Preferably, described preparation method, the described redox reaction condition of its step (2) is 70 degrees Celsius of constant temperature, and the reaction time is 1 hour, and described externally-applied magnetic field intensity is 0.4 tesla.
According to another aspect of the present invention, a kind of NiO/Ni self-supported membrane is provided, there is the Ni nano wire of NiO on the surface that the Ni nano wire described in comprising and calcining thereof make, and wherein the molar ratio of Ni and NiO is 2.5:1 to 20:1.
According to another aspect of the present invention, a kind of preparation method of NiO/Ni self-supported membrane is provided, comprise the following steps:
(a) Ni nano wire as claimed in claim 1 is dispersed in surfactant organic solution, forms Ni nano wire dispersion liquid;
(b) by the Ni nano wire dispersion liquid making in step (a), adopt the method for suction filtration, transfer on miillpore filter, after cleaning, drying, peel off and obtain Ni self-supported membrane;
(c) the Ni self-supported membrane making in step (b) is calcined and obtained NiO/Ni self-supported membrane in oxygenous atmosphere.
Preferably, described NiO/Ni self-supported membrane preparation method, the ethylene glycol solution of the polyvinylpyrrolidone that the described surfactant organic solution of its step (a) is 1wt%, described Ni nano wire and organic solution mass ratio are between 1:1000 to 1:2500, and described process for dispersing adopts 100 watts of ultrasonic dispersions 10 minutes.
Preferably, described NiO/Ni self-supported membrane preparation method, the described oxygenous atmosphere of its step (c) is air atmosphere, 350 degrees Celsius to 450 degrees Celsius of calcining heats, calcining annealing time 3 minutes to 10 minutes.
NiO/Ni self-supported membrane provided by the invention can be used as the active material of super capacitor.
In general, the above technical scheme of conceiving by the present invention compared with prior art, because overlength Ni nano wire provided by the invention can be prepared the good NiO/Ni self-supported membrane of pliability, be applied to super capacitor electrode active material, can obtain following beneficial effect:
(1) Ni nano wire provided by the invention, its length is 50,000nm to 200, between 000nm, be greatly longer than common Ni nano wire, as the raw material of self-supported membrane, can increase the pliability of self-supported membrane, as capacitance electrode active material, there is good chemical property.
(2) overlength Ni nano wire manufacture method provided by the invention, adopts externally-applied magnetic field, does not affect the chemical reaction that Ni simple substance generates.Along under magneticaction, adopt liquid-phase growth method, can obtain the Ni nano wire of overlength.Meanwhile, its process units is simple, can on current Ni nano wire process units, improve and obtain easily.
(3) NiO/Ni self-supported membrane provided by the invention, wherein the molar ratio of Ni and NiO is controlled, can meet the requirement of different super capacitors to electrode material.Its toughness is strong, applies the super capacitor that NiO/Ni self-supported membrane provided by the invention is made, and can be applied to wearable electronic, is the ideal electrode material of super capacitor in future.NiO/Ni self-supported membrane provided by the invention, has good transferability, and convenient processing, is applicable to large-scale industrial production.
(4) preparation method of NiO/Ni self-supported membrane provided by the invention, can, by different calcining heats and annealing time, control the component ratio of Ni and NiO, thereby adjust its chemical property and other physicochemical properties.The preparation method of NiO/Ni self-supported membrane provided by the invention, the advantages of nontoxic raw materials that it adopts, the technique of employing is simple, is applied to industrial mass production, can the cheap super capacitor electrode active material of cost of manufacture.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of Ni nano wire sample provided by the invention;
Fig. 2 is the XRD figure of Ni nano wire sample provided by the invention;
Fig. 3 is the scanning electron microscope (SEM) photograph in Ni nano wire self-supported membrane provided by the invention cross section;
Fig. 4 is NiO/Ni self-supported membrane sample drawing provided by the invention;
Fig. 5 is Ni nano wire scanning electron microscope (SEM) photograph provided by the invention;
Fig. 6 is the photo of NiO/Ni self-supported membrane provided by the invention;
Fig. 7 is that NiO/Ni self-supported membrane provided by the invention is as work electrode photo;
Fig. 8 be NiO/Ni self-supported membrane provided by the invention as work electrode the charging and discharging curve under different current densities;
Fig. 9 is the electrochemical impedance spectroscopy of NiO/Ni self-supported membrane provided by the invention as work electrode;
Figure 10 is the XRD picture of embodiment sample;
Figure 11 is that the NiO/Ni self-supported membrane that provides of each embodiment is as work electrode, at 50mVs -1sweep the cyclic voltammetry curve under speed.
In institute's drawings attached, identical Reference numeral is used for representing identical element or structure, wherein:
Fig. 4 (a) is that Ni nano wire is evenly distributed on miillpore filter after suction filtration; Fig. 4 (b) is Ni nano wire self-supported membrane; Fig. 4 (c) is the Ni self-supported membrane that is cut into 1x1cm;
Fig. 5 (a) is the NiO/Ni self-supported membrane Sample Scan Electronic Speculum figure of embodiment 2; Fig. 5 (b) is the NiO/Ni self-supported membrane Sample Scan Electronic Speculum figure of embodiment 3; Fig. 5 (c) is the NiO/Ni self-supported membrane Sample Scan Electronic Speculum figure of embodiment 1;
Figure 10 (a) curve is the NiO/Ni self-supported membrane XRD figure that embodiment 2 provides; Figure 10 (b) curve is the NiO/Ni self-supported membrane XRD figure that embodiment 3 provides; Figure 10 (c) curve is the NiO/Ni self-supported membrane XRD figure that embodiment 1 provides.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.In addition,, in each execution mode of described the present invention, involved technical characterictic just can combine mutually as long as do not form each other conflict.
Ni nano wire provided by the invention, average diameter is between 200nm to 300nm, and average length is 50,000nm to 200,000nm.Its transmission electron microscope picture, as shown in Figure 1.Its XRD(X x ray diffraction analysis x) picture, as shown in Figure 2, the material that shows synthesized is pure Ni.
Ni nano wire provided by the invention, its preparation method comprises the following steps:
(1) configuration Ni nano wire liquid growth liquid.
Using Ni salt as presoma, for example Nickel dichloride hexahydrate (NiCl 26H 2o), be dissolved in organic solvent ethylene glycol, make Ni precursor solution, while adopting Nickel dichloride hexahydrate to make Ni precursor solution, concentration is 24mg/ml.
Organic reducing agent, as hydrazine hydrate is dissolved in organic solvent ethylene glycol, is made to reductant solution, and the concentration of the ethylene glycol solution of hydrazine hydrate is 85wt%.
Ni precursor solution is slowly scattered in strong basicity organic solvent, is preferably the NaOH ethylene glycol solution of 1.5mol/L, Ni precursor solution drop by drop adds in strong basicity organic solvent and evenly and mixes.Then add reductant solution, finally add surfactant solution, as the polyvinylpyrrolidonesolution solution that concentration is 2wt%, make Ni nano wire liquid growth liquid.The mixed proportion of described Ni precursor solution, strong basicity organic solution, reducing agent organic solution is volume ratio 1:4:2.
(2) redox reaction is prepared Ni nano wire.
Under externally-applied magnetic field, control temperature constant condition and make Ni nano wire liquid growth liquid generation redox reaction, preparation Ni nano wire simple substance.Preferably, reaction temperature is 70 degrees Celsius of constant temperature, 1 hour reaction time, externally-applied magnetic field intensity 0.4 tesla.
(3) separate Ni nano wire simple substance.
First Magnetic Isolation Ni nano wire: utilize magnet that the Ni nano wire of generation is transferred in clean container; Then clean Ni nano wire: clean respectively 3 times with deionized water, absolute ethyl alcohol; Final drying Ni nano wire: in vacuum drying chamber, 60 degrees Celsius are dried 12 hours, make pure Ni nano wire simple substance.
NiO/Ni self-supported membrane provided by the invention, comprises described Ni nano wire and with described Ni nano wire, calcines the NiO/Ni nano wire making, in described NiO/Ni nano wire composite material, the molar ratio of Ni and NiO is 2.5:1 to 20:1.Its performance of the thickness effect of described NiO/Ni self-supported membrane, too thin intensity is lower, and too thick its conductivity is affected.Preferably, described NiO/Ni self-supported membrane thickness is between 25 μ m to 30 μ m, as shown in Figure 3.
NiO/Ni self-supported membrane provided by the invention, its preparation method, comprises the following steps:
(a) described Ni nano wire is dispersed in surfactant organic solution.
Described Ni nano wire is dispersed in surfactant organic solution, makes Ni nano wire dispersion liquid, the ethylene glycol solution that preferred surfactant organic solution is polyvinylpyrrolidone, concentration is 1wt%.Described Ni nano wire and organic solvent mass ratio are between 1:1000 to 1:2500.For making Ni nano wire dispersed, adopt the supersonic wave cleaning machine of 100 watts, to the ultrasonic dispersion of Ni nano wire dispersion liquid 10 minutes.
(b) Ni nano wire dispersion liquid suction filtration is made to Ni self-supported membrane.
By the Ni nano wire dispersion liquid making in step (a), adopt the method for suction filtration, transfer on miillpore filter.Repeatedly clean the Ni self-supported membrane on miillpore filter with deionized water, then use 60 degrees Celsius of vacuumizes of vacuum drying chamber 5 hours, after peeling off, make Ni self-supported membrane.Described Ni self-supported membrane pattern, as shown in Figure 4, wherein Fig. 4 (a) is evenly distributed on miillpore filter for Ni nano wire after suction filtration; Fig. 4 (b) is Ni nano wire self-supported membrane photo; Fig. 4 (c) is for being cut into the Ni self-supported membrane of 1x1cm; Fig. 4 (d) is the scanning electron microscope (SEM) photograph of Ni nano wire under low multiplication factor.
(c) in oxygen-containing atmosphere, calcine Ni self-supported membrane and make NiO/Ni self-supported membrane.
The Ni self-supported membrane making in step (b) is calcined in oxygen-containing atmosphere to generally calcining under air atmosphere, 350 degrees Celsius to 450 degrees Celsius of calcining heats, calcining annealing time 3 minutes to 10 minutes.As shown in Figure 5, calcining heat is higher, and the crystal type of NiO is better, obtains the different NiO/Ni self-supported membrane of component ratio under different calcining heats.
NiO/Ni self-supported membrane provided by the invention, has good pliability, as shown in Figure 6.Described NiO/Ni self-supported membrane, as work electrode, as shown in Figure 7, and charging and discharging curve under its different current densities, as shown in Figure 8, its impedance spectrum as shown in Figure 9, confirms to have good capacitive property through experiment, can be used as the active material of super capacitor.
Be below embodiment:
Embodiment 1
A kind of Ni nano wire, average diameter is 250nm, average length is 100,000nm.
The preparation method of described Ni nano wire, comprises the following steps:
(1) configuration Ni nano wire liquid growth liquid.
By Nickel dichloride hexahydrate (NiCl 26H 2o), be dissolved in ethylene glycol, make Ni precursor solution, concentration is 24mg/ml.
Hydrazine hydrate is dissolved in ethylene glycol, makes reductant solution, concentration is 85wt%.
Ni precursor solution is drop by drop added in the NaOH ethylene glycol of 1.5mol/L, evenly mix.Then add reductant solution, finally adding concentration is the polyvinylpyrrolidonesolution solution solution of 2wt%, makes Ni nano wire liquid growth liquid.The mixed proportion of described Ni precursor solution, strong basicity organic solution, reducing agent organic solution is volume ratio 1:4:2.
(2) redox reaction is prepared Ni nano wire.
The Ni nano wire liquid growth liquid preparing in step (1) is transferred in clean beaker, then it is sealed with preservative film, and on diaphragm seal, stay a little apertures.Beaker is put into constant temperature water bath apparatus, under the externally-applied magnetic field of 0.4 tesla, 70 degrees Celsius of reactions 1 hour.
(3) separate Ni nano wire simple substance.
First Magnetic Isolation Ni nano wire: utilize magnet that the Ni nano wire of generation is transferred in clean container; Then clean Ni nano wire: clean respectively 3 times with deionized water, absolute ethyl alcohol; Final drying Ni nano wire: in vacuum drying chamber, 60 degrees Celsius are dried 12 hours, make pure Ni nano wire simple substance.
A kind of NiO/Ni self-supported membrane, comprises described Ni nano wire and with described Ni nano wire, calcines the NiO/Ni composite material making, in described NiO/Ni composite material, Ni and NiO molar ratio are: 2.5:1, described NiO/Ni self-supported membrane thickness is 25 μ m.Its XRD phenogram as shown in figure 10, the NiO/Ni self-supported membrane XRD diffraction curve that wherein c curve provides for the present embodiment.Its scanning electron microscope (SEM) photograph is as shown in Fig. 5 (c).
Described NiO/Ni self-supported membrane, its preparation method, comprises the following steps:
(a) described Ni nano wire is dispersed in surfactant organic solution.
Described Ni nano wire is dispersed in the ethylene glycol solution of polyvinylpyrrolidone that concentration is 1wt%, makes Ni nano wire dispersion liquid.Described Ni nano wire and organic solvent mass ratio are 1:1500.For making Ni nano wire dispersed, adopt the supersonic wave cleaning machine of 100 watts, to the ultrasonic dispersion of Ni nano wire dispersion liquid 10 minutes.
(b) Ni nano wire dispersion liquid suction filtration is made to Ni self-supported membrane.
By the Ni nano wire dispersion liquid making in step (a), adopt the method for suction filtration, transfer on miillpore filter.Repeatedly clean the Ni self-supported membrane on miillpore filter with deionized water, then use 60 degrees Celsius of vacuumizes of vacuum drying chamber 5 hours, after peeling off, make Ni self-supported membrane.
(c) in oxygen-containing atmosphere, calcine Ni self-supported membrane and make NiO/Ni self-supported membrane.
The Ni self-supported membrane making in step (b) is calcined under air atmosphere, 450 degrees Celsius of calcining heats, calcining annealing time 5 minutes, makes NiO/Ni self-supported membrane.
Described NiO/Ni self-supported membrane, has good pliability.Through experiment, confirm, described NiO/Ni self-supported membrane has good capacitive property, as shown in figure 11, can be used as the active material of super capacitor.
Embodiment 2
A kind of Ni nano wire, average diameter is 200nm, average length is 50,000nm.
The preparation method of described Ni nano wire, comprises the following steps:
(1) configuration Ni nano wire liquid growth liquid.
By Nickel dichloride hexahydrate (NiCl 26H 2o), be dissolved in ethylene glycol, make Ni precursor solution, concentration is 24mg/ml.
Hydrazine hydrate is dissolved in ethylene glycol, makes reductant solution, concentration is 85wt%.
Ni precursor solution is drop by drop added in the NaOH ethylene glycol of 1.5mol/L, evenly mix.Then add reductant solution, finally adding concentration is the polyvinylpyrrolidonesolution solution solution of 2wt%, makes Ni nano wire liquid growth liquid.The mixed proportion of described Ni precursor solution, strong basicity organic solution, reducing agent organic solution is volume ratio 1:4:2.
(2) redox reaction is prepared Ni nano wire.
The Ni nano wire liquid growth liquid preparing in step (1) is transferred in clean beaker, then it is sealed with preservative film, and on diaphragm seal, stay a little apertures.Beaker is put into constant temperature water bath apparatus, under the externally-applied magnetic field of 0.4 tesla, 70 degrees Celsius of reactions 1 hour.
(3) separate Ni nano wire simple substance.
First Magnetic Isolation Ni nano wire: utilize magnet that the Ni nano wire of generation is transferred in clean container; Then clean Ni nano wire: clean respectively 3 times with deionized water, absolute ethyl alcohol; Final drying Ni nano wire: in vacuum drying chamber, 60 degrees Celsius are dried 12 hours, make pure Ni nano wire simple substance.
A kind of NiO/Ni self-supported membrane, comprises described Ni nano wire and with described Ni nano wire, calcines the NiO/Ni composite material making, in described NiO/Ni composite material, Ni and NiO molar ratio are: 20:1, described NiO/Ni self-supported membrane thickness is 28 μ m.Its XRD phenogram as shown in figure 10, the NiO/Ni self-supported membrane XRD diffraction curve that wherein a curve provides for the present embodiment.Its scanning electron microscope (SEM) photograph is as shown in Fig. 5 (a).
Described NiO/Ni self-supported membrane, its preparation method, comprises the following steps:
(a) described Ni nano wire is dispersed in surfactant organic solution.
Described Ni nano wire is dispersed in the ethylene glycol solution of polyvinylpyrrolidone that concentration is 1wt%, makes Ni nano wire dispersion liquid.Described Ni nano wire and organic solvent mass ratio are 1:1000.For making Ni nano wire dispersed, adopt the supersonic wave cleaning machine of 100 watts, to the ultrasonic dispersion of Ni nano wire dispersion liquid 10 minutes.
(b) Ni nano wire dispersion liquid suction filtration is made to Ni self-supported membrane.
By the Ni nano wire dispersion liquid making in step (a), adopt the method for suction filtration, transfer on miillpore filter.Repeatedly clean the Ni self-supported membrane on miillpore filter with deionized water, then use 60 degrees Celsius of vacuumizes of vacuum drying chamber 5 hours, after peeling off, make Ni self-supported membrane.
(c) in oxygen-containing atmosphere, calcine Ni self-supported membrane and make NiO/Ni self-supported membrane.
The Ni self-supported membrane making in step (b) is calcined under air atmosphere, 350 degrees Celsius of calcining heats, calcining annealing time 3 minutes, makes NiO/Ni self-supported membrane.
Described NiO/Ni self-supported membrane, has good pliability.Through experiment, confirm, described NiO/Ni self-supported membrane has good capacitive property, as shown in figure 11, can be used as the active material of super capacitor.
Embodiment 3
A kind of Ni nano wire, average diameter is 300nm, average length is 200,000nm.
The preparation method of described Ni nano wire, comprises the following steps:
(1) configuration Ni nano wire liquid growth liquid.
By Nickel dichloride hexahydrate (NiCl 26H 2o), be dissolved in ethylene glycol, make Ni precursor solution, concentration is 24mg/ml.
Hydrazine hydrate is dissolved in ethylene glycol, makes reductant solution, concentration is 85wt%.
Ni precursor solution is drop by drop added in the NaOH ethylene glycol of 1.5mol/L, evenly mix.Then add reductant solution, finally adding concentration is the polyvinylpyrrolidonesolution solution solution of 2wt%, makes Ni nano wire liquid growth liquid.The mixed proportion of described Ni precursor solution, strong basicity organic solution, reducing agent organic solution is volume ratio 1:4:2.
(2) redox reaction is prepared Ni nano wire.
The Ni nano wire liquid growth liquid preparing in step (1) is transferred in clean beaker, then it is sealed with preservative film, and on diaphragm seal, stay a little apertures.Beaker is put into constant temperature water bath apparatus, under the externally-applied magnetic field of 0.4 tesla, 70 degrees Celsius of reactions 1 hour.
(3) separate Ni nano wire simple substance.
First Magnetic Isolation Ni nano wire: utilize magnet that the Ni nano wire of generation is transferred in clean container; Then clean Ni nano wire: clean respectively 3 times with deionized water, absolute ethyl alcohol; Final drying Ni nano wire: in vacuum drying chamber, 60 degrees Celsius are dried 12 hours, make pure Ni nano wire simple substance.
A kind of NiO/Ni self-supported membrane, comprises described Ni nano wire and with described Ni nano wire, calcines the NiO/Ni composite material that makes 1, in described NiO/Ni composite material, Ni and NiO molar ratio are 10:1, and described NiO/Ni self-supported membrane thickness is 30 μ m.Its XRD phenogram as shown in figure 10, the NiO/Ni self-supported membrane XRD diffraction curve that wherein b curve provides for the present embodiment.Its scanning electron microscope (SEM) photograph is as shown in Fig. 5 (b).
Described NiO/Ni self-supported membrane, its preparation method, comprises the following steps:
(a) described Ni nano wire is dispersed in surfactant organic solution.
Described Ni nano wire is dispersed in the ethylene glycol solution of polyvinylpyrrolidone that concentration is 1wt%, makes Ni nano wire dispersion liquid.Described Ni nano wire and organic solvent mass ratio are 1:2500.For making Ni nano wire dispersed, adopt the supersonic wave cleaning machine of 100 watts, to the ultrasonic dispersion of Ni nano wire dispersion liquid 10 minutes.
(b) Ni nano wire dispersion liquid suction filtration is made to Ni self-supported membrane.
By the Ni nano wire dispersion liquid making in step (a), adopt the method for suction filtration, transfer on miillpore filter.Repeatedly clean the Ni self-supported membrane on miillpore filter with deionized water, then use 60 degrees Celsius of vacuumizes of vacuum drying chamber 5 hours, after peeling off, make Ni self-supported membrane.
(c) in oxygen-containing atmosphere, calcine Ni self-supported membrane and make NiO/Ni self-supported membrane.
The Ni self-supported membrane making in step (b) is calcined under air atmosphere, 400 degrees Celsius of calcining heats, calcining annealing time 10 minutes, makes NiO/Ni self-supported membrane.
Described NiO/Ni self-supported membrane, has good pliability.Through experiment, confirm, described NiO/Ni self-supported membrane has good capacitive property, as shown in figure 11, can be used as the active material of super capacitor
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (9)

1. a Ni nano wire, is characterized in that, described Ni nano wire average diameter is between 200nm to 300nm, and average length is 50, and 000nm to 200, between 000nm.
2. the preparation method of Ni nano wire as claimed in claim 1, is characterized in that, comprises the following steps:
(1) configuration Ni nano wire liquid growth liquid: using Ni salt as presoma, be dissolved in organic solvent, make Ni precursor solution; Organic reducing agent is dissolved in described organic solvent, makes reductant solution; Ni precursor solution is slowly scattered in strong basicity organic solvent, then adds reductant solution, finally add surfactant organic solution, make Ni nano wire liquid growth liquid;
(2), under externally-applied magnetic field, make Ni nano wire liquid growth liquid generation redox reaction, preparation Ni nano wire simple substance;
(3) Magnetic Isolation clean Ni nano wire simple substance, makes Ni nano wire as claimed in claim 1 after dry.
3. preparation method as claimed in claim 2, is characterized in that, the described Ni salt of step (1) is Nickel dichloride hexahydrate, and described organic solvent is ethylene glycol, and described Ni precursor solution concentration is 24mg/ml; Described organic reducing agent is hydrazine hydrate, and described organic reducing agent solution concentration is 85wt%; The NaOH ethylene glycol solution that described strong basicity organic solvent is 1.5mol/L; The polyvinylpyrrolidone that described surfactant organic solution is 2wt%; The mixed proportion of described Ni precursor solution, strong basicity organic solution, reducing agent organic solution is volume ratio 1:4:2.
4. preparation method as claimed in claim 2, is characterized in that, the described redox reaction condition of step (2) is 70 degrees Celsius of constant temperature, and the reaction time is 1 hour, and described externally-applied magnetic field intensity is 0.4 tesla.
5. a NiO/Ni self-supported membrane, is characterized in that, comprises that there is the Ni nano wire of NiO on surface that Ni nano wire as claimed in claim 1 and calcining thereof make, and wherein the molar ratio of Ni and NiO is 2.5:1 to 20:1.
6. the preparation method of NiO/Ni self-supported membrane as claimed in claim 5, is characterized in that, comprises the following steps:
(a) Ni nano wire as claimed in claim 1 is dispersed in surfactant organic solution, forms Ni nano wire dispersion liquid;
(b) by the Ni nano wire dispersion liquid making in step (a), adopt the method for suction filtration, transfer on miillpore filter, after cleaning, drying, peel off and obtain Ni self-supported membrane;
(c) the Ni self-supported membrane making in step (b) is calcined and obtained NiO/Ni self-supported membrane in oxygenous atmosphere.
7. preparation method as claimed in claim 6, it is characterized in that, the ethylene glycol solution of the polyvinylpyrrolidone that the described surfactant organic solution of step (a) is 1wt%, described Ni nano wire and organic solution mass ratio are between 1:1000 to 1:2500, and described process for dispersing adopts 100 watts of ultrasonic dispersions 10 minutes.
8. preparation method as claimed in claim 6, is characterized in that, the described oxygenous atmosphere of step (c) is air atmosphere, 350 degrees Celsius to 450 degrees Celsius of calcining heats, calcining annealing time 3 minutes to 10 minutes.
9. NiO/Ni self-supported membrane as claimed in claim 5 can be used as the active material of super capacitor.
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CN109904001A (en) * 2019-04-10 2019-06-18 蚌埠学院 A kind of nano combined electrode material for super capacitor of nickel oxide/nickel and preparation method thereof
CN111554501A (en) * 2020-04-28 2020-08-18 天津大学 Preparation method of superparamagnetic nickel nanoparticles for magnetically adsorbing bacteria and spores
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