CN103762356B - Ni nano wire, NiO/Ni self-supported membrane and its preparation method and application - Google Patents
Ni nano wire, NiO/Ni self-supported membrane and its preparation method and application Download PDFInfo
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- CN103762356B CN103762356B CN201310740240.0A CN201310740240A CN103762356B CN 103762356 B CN103762356 B CN 103762356B CN 201310740240 A CN201310740240 A CN 201310740240A CN 103762356 B CN103762356 B CN 103762356B
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Abstract
The invention discloses a kind of Ni nano wire, NiO/Ni self-supported membrane and its preparation method and application.Described Ni nano wire is the overlong nanowire of average length 50,000 to 200,000nm；Its preparation method is: first configuration Ni nano wire liquid growth liquid；Then under externally-applied magnetic field, prepare Ni nano wire simple substance；It is finally separating purification Ni nano wire.Described NiO/Ni self-supported membrane includes the Ni nano wire that surface is NiO that described Ni nano wire and calcining thereof prepare；Its preparation method is: be first dispersed in surfactant solution by described Ni nano wire；Then Ni nano wire is transferred on microporous filter membrane by sucking filtration, prepares Ni self-supported membrane；Finally calcining under Ni self-supported membrane oxygen-containing atmosphere is obtained NiO/Ni self-supported membrane.The NiO/Ni self-supported membrane that the present invention provides, pliability and chemical property are good, can be as super capacitor active material, and low cost, technique is simple.
Description
Technical field
The invention belongs to field of nanometer material technology, more particularly, to a kind of Ni nano wire, NiO/Ni self-supported membrane and its preparation method and application.
Background technology
Gradually use up totally along with traditional fossil energy, there is the new forms of energy such as solar energy, wind energy, nuclear energy, geothermal energy etc. of the advantage such as environmental protection, recyclability receive people and more and more pay close attention to and develop, apply, and new forms of energy are frequently present of the problem of an electrical power storage during generating electricity by way of merging two or more grid systems, and perhaps the advantage that ultracapacitor is in terms of energy storage can well solve these problems.
Yuan et al. has delivered one with MnO at nature nanotechnology in 20082Based on self-supported membrane, then reach the purpose of hydrophobic/hydrophilic by de-agglomerate dimethyl siloxane (PDMS) at absorption at 234 DEG C and 390 DEG C, in terms of absorption greasy dirt, there is huge application potential.Luo et al. has obtained CNT/LiCoO in 2012 by the method simply overlength, super neat CNT being carried out ultrasonic codeposition with lithium cobalt oxide micron particle2The self-supported membrane that composite is constituted, the lithium ion cell positive being different from routine needs to add extra conductive agent (such 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 preferable performance of lithium ion battery.Yuan et al. with graphene oxide/carbon nano-tube film as substrate, then went out ultracapacitor active substance Co by the hydro-thermal reaction face direct growth on the composite of 14 hours at 90 DEG C in 20123O4, at 2Ag-1Charging and discharging currents density under obtain 378Fg-1Ratio electric capacity, there is fabulous pliability simultaneously.
Metal-oxide based capacitor is studied the most successfully electrode material at present and is mainly ruthenium-oxide, but the resource-constrained due to noble metal, selling at exorbitant prices limits the use to it, the research of metal oxide capacitor is essentially consisted in the cost reducing material, finds more cheap material.
Summary of the invention
Disadvantages described above or Improvement requirement for prior art, the invention provides a kind of Ni nano wire, NiO/Ni self-supported membrane and its preparation method and application, pliability is good, charge-discharge performance is excellent and lower-cost super capacitor electrode active material to its object is to provide one, thus solves current super capacitor cost height, the technical problem of complex manufacturing technology.
For achieving the above object, according to one aspect of the present invention, it is provided that 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.
It is another aspect of this invention to provide that provide the preparation method of a kind of Ni nano wire, comprise the following steps:
(1) configuration Ni nano wire liquid growth liquid: using Ni salt as presoma, be dissolved in organic solvent, prepares Ni precursor solution；Organic reducing agent is dissolved in described organic solvent, prepares reductant solution；Ni precursor solution is slowly scattered in strong basicity organic solvent, adds reductant solution, be eventually adding surfactant organic solution, prepare Ni nano wire liquid growth liquid；
(2) under externally-applied magnetic field, make Ni nano wire liquid growth liquid generation redox reaction, prepare Ni nano wire simple substance；
(3) Magnetic Isolation clean Ni nano wire simple substance, dried prepares Ni nano wire as claimed in claim 1.
Preferably, described preparation method, the Ni salt described in 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%；Described strong basicity organic solvent is the sodium hydroxide ethylene glycol solution of 1.5mol/L；Described surfactant organic solution is the polyvinylpyrrolidone of 2wt%；Described Ni precursor solution, strong basicity organic solution, the mixed proportion of reducing agent organic solution are volume ratio 1:4:2.
Preferably, described preparation method, the redox reaction condition described in its step (2) is 70 degrees Celsius of constant temperature, and the response time is 1 hour, and described applied field strengths is 0.4 tesla.
According to another aspect of the present invention, it is provided that a kind of NiO/Ni self-supported membrane, having the Ni nano wire of NiO including the surface that described Ni nano wire and calcining thereof are prepared, wherein the molar ratio of Ni and NiO is 2.5:1 to 20:1.
According to another aspect of the present invention, it is provided that the preparation method of a kind of NiO/Ni self-supported membrane, comprise the following steps:
A Ni nano wire as claimed in claim 1 is dispersed in surfactant organic solution by (), form Ni nanowire dispersion；
B Ni nanowire dispersion that () will prepare in step (a), the method using sucking filtration, transfer on microporous filter membrane, peel off after cleaning, drying and obtain Ni self-supported membrane；
C the Ni self-supported membrane prepared in step (b) is calcined in oxygenous atmosphere and is obtained NiO/Ni self-supported membrane by ().
Preferably, described NiO/Ni self-supported membrane preparation method, the ethylene glycol solution of the polyvinylpyrrolidone that surfactant organic solution is 1wt% described in its step (a), described Ni nano wire and organic solution mass ratio are between 1:1000 to 1:2500, and described process for dispersing uses 100 watts of ultrasonic disperse 10 minutes.
Preferably, described NiO/Ni self-supported membrane preparation method, the oxygenous atmosphere described in its step (c) is air atmosphere, calcining heat 350 degrees Celsius to 450 degrees Celsius, calcining annealing time 3 minutes to 10 minutes.
The NiO/Ni self-supported membrane that the present invention provides can be used as the active substance of super capacitor.
In general, by the contemplated above technical scheme of the present invention compared with prior art, the overlength Ni nano wire provided due to the present invention can prepare the NiO/Ni self-supported membrane that pliability is good, is applied to super capacitor electrode active material, it is possible to obtains following beneficial effect:
(1) present invention provide Ni nano wire, its length 50,000nm to 200, between 000nm, it is significantly longer than common Ni nano wire, as the raw material of self-supported membrane, the pliability of self-supported membrane can be increased, as capacitance electrode active material, there is excellent chemical property.
(2) the overlength Ni nano wire manufacture method that the present invention provides, uses externally-applied magnetic field, does not affect the chemical reaction that Ni simple substance generates.Under along magneticaction, use liquid-phase growth method, the Ni nano wire of overlength can be obtained.Meanwhile, its process units is simple, can improve easily and obtain on current Ni nano wire process units.
(3) the NiO/Ni self-supported membrane that the present invention provides, wherein the molar ratio of Ni and NiO is controlled, can meet the requirement to electrode material of the different super capacitors.Its toughness is strong, the super capacitor that the NiO/Ni self-supported membrane that the application present invention provides makes, it is possible to be applied to wearable electronic, is the ideal electrode material of super capacitor in the future.The NiO/Ni self-supported membrane that the present invention provides, has good transferability, convenient processing, is suitable for large-scale industrial production.
(4) preparation method of the NiO/Ni self-supported membrane that the present invention provides, by different calcining heats and annealing time, can control the component ratio of Ni and NiO, thus adjust its chemical property and other physicochemical properties.The preparation method of the NiO/Ni self-supported membrane that the present invention provides, its advantages of nontoxic raw materials used, the technique of employing is simple, is applied to industrial mass production, the super capacitor electrode active material that energy cost of manufacture is cheap.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the Ni nano wire sample that the present invention provides；
Fig. 2 is the XRD figure of the Ni nano wire sample that the present invention provides；
Fig. 3 is the scanning electron microscope (SEM) photograph in the Ni nano wire self-supported membrane cross section that the present invention provides；
Fig. 4 is the NiO/Ni self-supported membrane sample drawing that the present invention provides；
Fig. 5 is the Ni nano wire scanning electron microscope (SEM) photograph that the present invention provides；
Fig. 6 is the photo of the NiO/Ni self-supported membrane that the present invention provides；
Fig. 7 is that the NiO/Ni self-supported membrane that provides of the present invention is as working electrode photo；
Fig. 8 is the NiO/Ni self-supported membrane that provides of the present invention as working electrode charging and discharging curve under different electric current densities；
Fig. 9 is the NiO/Ni self-supported membrane that provides of the present invention electrochemical impedance spectroscopy as working electrode；
Figure 10 is the XRD figure sheet of embodiment sample；
Figure 11 be each embodiment provide NiO/Ni self-supported membrane as working electrode, at 50mVs-1Sweep the cyclic voltammetry curve under speed.
In all of the figs, identical reference is used for representing identical element or structure, wherein:
Fig. 4 (a) is that Ni nano wire is evenly distributed on microporous filter membrane after sucking filtration；Fig. 4 (b) is Ni nano wire self-supported membrane；Fig. 4 (c) is the Ni self-supported membrane being 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.
Detailed description of the invention
In order to make the purpose 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.As long as just can be mutually combined additionally, technical characteristic involved in each embodiment of invention described below does not constitutes conflict each other.
The Ni nano wire that the present invention provides, 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 in figure 2 it is shown, show that synthesized material is pure Ni.
The Ni nano wire that the present invention provides, its preparation method comprises the following steps:
(1) configuration Ni nano wire liquid growth liquid.
Using Ni salt as presoma, such as Nickel dichloride hexahydrate (NiCl2·6H2O), being dissolved in organic solvent ethylene glycol, prepare Ni precursor solution, when using Nickel dichloride hexahydrate to make Ni precursor solution, concentration is 24mg/ml.
Being dissolved in organic solvent ethylene glycol by organic reducing agent such as hydrazine hydrate, prepare reductant solution, the concentration of the ethylene glycol solution of hydrazine hydrate is 85wt%.
Slowly being scattered in strong basicity organic solvent by Ni precursor solution, the sodium hydroxide ethylene glycol solution of preferably 1.5mol/L, Ni precursor solution drop by drop adds in strong basicity organic solvent and uniformly mixes.It is subsequently adding reductant solution, is eventually adding surfactant solution, if concentration is the polyvinylpyrrolidonesolution solution of 2wt%, i.e. prepare Ni nano wire liquid growth liquid.Described Ni precursor solution, strong basicity organic solution, the mixed proportion of reducing agent organic solution are volume ratio 1:4:2.
(2) redox reaction prepares Ni nano wire.
Under externally-applied magnetic field, control temperature constant condition and make Ni nano wire liquid growth liquid generation redox reaction, prepare Ni nano wire simple substance.Preferably, reaction temperature is 70 degrees Celsius of constant temperature, 1 hour response time, applied field strengths 0.4 tesla.
(3) Ni nano wire simple substance is separated.
First Magnetic Isolation Ni nano wire: utilize Magnet to be transferred in clean container by the Ni nano wire of generation；Then Ni nano wire is cleaned: be respectively washed 3 times with deionized water, dehydrated alcohol；Finally being dried Ni nano wire: in vacuum drying oven, 60 degrees Celsius are dried 12 hours, i.e. prepare pure Ni nano wire simple substance.
The NiO/Ni self-supported membrane that the present invention provides, calcines prepared NiO/Ni nano wire including described Ni nano wire and with described Ni nano wire, and in described NiO/Ni nanowire composite, the molar ratio of Ni and NiO is 2.5:1 to 20:1.Its performance of thickness effect of described NiO/Ni self-supported membrane, the thinnest then intensity is relatively low, and its electric conductivity the thickest is affected.Preferably, described NiO/Ni self-supported membrane thickness is between 25 μm to 30 μm, as shown in Figure 3.
The NiO/Ni self-supported membrane that the present invention provides, its preparation method, comprise the following steps:
A described Ni nano wire is dispersed in surfactant organic solution by ().
Being dispersed in surfactant organic solution by described Ni nano wire, prepare Ni nanowire dispersion, preferred surfactant organic solution is the ethylene glycol solution of polyvinylpyrrolidone, and 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, use the ultrasonic washing unit of 100 watts, to Ni nanowire dispersion ultrasonic disperse 10 minutes.
B Ni nanowire dispersion sucking filtration is prepared Ni self-supported membrane by ().
The Ni nanowire dispersion that will prepare in step (a), the method using sucking filtration, transfer on microporous filter membrane.Repeatedly clean the Ni self-supported membrane on microporous filter membrane with deionized water, be then vacuum dried 5 hours with 60 degrees Celsius of vacuum drying oven, after stripping, i.e. prepare Ni self-supported membrane.Described Ni self-supported membrane pattern, as shown in Figure 4, wherein Fig. 4 (a) is that Ni nano wire is evenly distributed on microporous filter membrane after sucking filtration；Fig. 4 (b) is Ni nano wire self-supported membrane photo；Fig. 4 (c) is the Ni self-supported membrane being cut into 1x1cm.
C () oxygen-containing atmosphere is calcined Ni self-supported membrane prepare NiO/Ni self-supported membrane.
The Ni self-supported membrane prepared in step (b) is calcined in oxygen-containing atmosphere, calcines the most in air atmosphere, calcining heat 350 degrees Celsius to 450 degrees Celsius, calcining annealing time 3 minutes to 10 minutes.As it is shown in figure 5, calcining heat is the highest, the crystal type of NiO is the best, obtains the NiO/Ni self-supported membrane that component ratio is different under different calcining heats.
The NiO/Ni self-supported membrane that the present invention provides, has good pliability, as shown in Figure 6.Described NiO/Ni self-supported membrane, as working electrode, as it is shown in fig. 7, charging and discharging curve under its different electric current densities, as shown in Figure 8, its impedance spectrum, as it is shown in figure 9, be verified by experiments and have good capacitive property, can be used as the active substance of super capacitor.
It is below embodiment:
Embodiment 1
A kind of Ni nano wire, average diameter is 250nm, and 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 (NiCl2·6H2O), being dissolved in ethylene glycol, prepare Ni precursor solution, concentration is 24mg/ml.
Being dissolved in ethylene glycol by hydrazine hydrate, prepare reductant solution, concentration is 85wt%.
Ni precursor solution is drop by drop added in the sodium hydroxide ethylene glycol of 1.5mol/L, uniformly mix.It is subsequently adding reductant solution, is eventually adding the polyvinylpyrrolidonesolution solution solution that concentration is 2wt%, i.e. prepare Ni nano wire liquid growth liquid.Described Ni precursor solution, strong basicity organic solution, the mixed proportion of reducing agent organic solution are volume ratio 1:4:2.
(2) redox reaction prepares Ni nano wire.
The Ni nano wire liquid growth liquid prepared in step (1) is transferred in clean beaker, then it is sealed with preservative film, and on diaphragm seal, stay a little aperture.Being put into by beaker in constant temperature water bath apparatus, under the externally-applied magnetic field of 0.4 tesla, 70 degrees Celsius are reacted 1 hour.
(3) Ni nano wire simple substance is separated.
First Magnetic Isolation Ni nano wire: utilize Magnet to be transferred in clean container by the Ni nano wire of generation；Then Ni nano wire is cleaned: be respectively washed 3 times with deionized water, dehydrated alcohol；Finally being dried Ni nano wire: in vacuum drying oven, 60 degrees Celsius are dried 12 hours, i.e. prepare pure Ni nano wire simple substance.
A kind of NiO/Ni self-supported membrane, calcines prepared NiO/Ni composite including described Ni nano wire and with described Ni nano wire, and in described NiO/Ni composite, Ni and NiO molar ratio is: 2.5:1, and described NiO/Ni self-supported membrane thickness is 25 μm.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.Shown in its scanning electron microscope (SEM) photograph such as Fig. 5 (c).
Described NiO/Ni self-supported membrane, its preparation method, comprise the following steps:
A described Ni nano wire is dispersed in surfactant organic solution by ().
Described Ni nano wire is dispersed in the ethylene glycol solution of the polyvinylpyrrolidone that concentration is 1wt%, prepares Ni nanowire dispersion.Described Ni nano wire and organic solvent mass ratio are 1:1500.For making Ni nano wire dispersed, use the ultrasonic washing unit of 100 watts, to Ni nanowire dispersion ultrasonic disperse 10 minutes.
B Ni nanowire dispersion sucking filtration is prepared Ni self-supported membrane by ().
The Ni nanowire dispersion that will prepare in step (a), the method using sucking filtration, transfer on microporous filter membrane.Repeatedly clean the Ni self-supported membrane on microporous filter membrane with deionized water, be then vacuum dried 5 hours with 60 degrees Celsius of vacuum drying oven, after stripping, i.e. prepare Ni self-supported membrane.
C () oxygen-containing atmosphere is calcined Ni self-supported membrane prepare NiO/Ni self-supported membrane.
The Ni self-supported membrane prepared in step (b) is calcined in air atmosphere, calcining heat 450 degrees Celsius, calcining annealing time 5 minutes, i.e. prepare NiO/Ni self-supported membrane.
Described NiO/Ni self-supported membrane, has good pliability.Being verified by experiments, described NiO/Ni self-supported membrane has good capacitive property, as shown in figure 11, can be used as the active substance of super capacitor.
Embodiment 2
A kind of Ni nano wire, average diameter is 200nm, and 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 (NiCl2·6H2O), being dissolved in ethylene glycol, prepare Ni precursor solution, concentration is 24mg/ml.
Being dissolved in ethylene glycol by hydrazine hydrate, prepare reductant solution, concentration is 85wt%.
Ni precursor solution is drop by drop added in the sodium hydroxide ethylene glycol of 1.5mol/L, uniformly mix.It is subsequently adding reductant solution, is eventually adding the polyvinylpyrrolidonesolution solution solution that concentration is 2wt%, i.e. prepare Ni nano wire liquid growth liquid.Described Ni precursor solution, strong basicity organic solution, the mixed proportion of reducing agent organic solution are volume ratio 1:4:2.
(2) redox reaction prepares Ni nano wire.
The Ni nano wire liquid growth liquid prepared in step (1) is transferred in clean beaker, then it is sealed with preservative film, and on diaphragm seal, stay a little aperture.Being put into by beaker in constant temperature water bath apparatus, under the externally-applied magnetic field of 0.4 tesla, 70 degrees Celsius are reacted 1 hour.
(3) Ni nano wire simple substance is separated.
First Magnetic Isolation Ni nano wire: utilize Magnet to be transferred in clean container by the Ni nano wire of generation；Then Ni nano wire is cleaned: be respectively washed 3 times with deionized water, dehydrated alcohol；Finally being dried Ni nano wire: in vacuum drying oven, 60 degrees Celsius are dried 12 hours, i.e. prepare pure Ni nano wire simple substance.
A kind of NiO/Ni self-supported membrane, calcines including described Ni nano wire and with described Ni nano wire
The NiO/Ni composite prepared, in described NiO/Ni composite, Ni and NiO molar ratio is: 20:1, and described NiO/Ni self-supported membrane thickness is 28 μm.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.Shown in its scanning electron microscope (SEM) photograph such as Fig. 5 (a).
Described NiO/Ni self-supported membrane, its preparation method, comprise the following steps:
A described Ni nano wire is dispersed in surfactant organic solution by ().
Described Ni nano wire is dispersed in the ethylene glycol solution of the polyvinylpyrrolidone that concentration is 1wt%, prepares Ni nanowire dispersion.Described Ni nano wire and organic solvent mass ratio are 1:1000.For making Ni nano wire dispersed, use the ultrasonic washing unit of 100 watts, to Ni nanowire dispersion ultrasonic disperse 10 minutes.
B Ni nanowire dispersion sucking filtration is prepared Ni self-supported membrane by ().
The Ni nanowire dispersion that will prepare in step (a), the method using sucking filtration, transfer on microporous filter membrane.Repeatedly clean the Ni self-supported membrane on microporous filter membrane with deionized water, be then vacuum dried 5 hours with 60 degrees Celsius of vacuum drying oven, after stripping, i.e. prepare Ni self-supported membrane.
C () oxygen-containing atmosphere is calcined Ni self-supported membrane prepare NiO/Ni self-supported membrane.
The Ni self-supported membrane prepared in step (b) is calcined in air atmosphere, calcining heat 350 degrees Celsius, calcining annealing time 3 minutes, i.e. prepare NiO/Ni self-supported membrane.
Described NiO/Ni self-supported membrane, has good pliability.Being verified by experiments, described NiO/Ni self-supported membrane has good capacitive property, as shown in figure 11, can be used as the active substance of super capacitor.
Embodiment 3
A kind of Ni nano wire, average diameter is 300nm, and 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 (NiCl2·6H2O), being dissolved in ethylene glycol, prepare Ni precursor solution, concentration is 24mg/ml.
Being dissolved in ethylene glycol by hydrazine hydrate, prepare reductant solution, concentration is 85wt%.
Ni precursor solution is drop by drop added in the sodium hydroxide ethylene glycol of 1.5mol/L, uniformly mix.It is subsequently adding reductant solution, is eventually adding the polyvinylpyrrolidonesolution solution solution that concentration is 2wt%, i.e. prepare Ni nano wire liquid growth liquid.Described Ni precursor solution, strong basicity organic solution, the mixed proportion of reducing agent organic solution are volume ratio 1:4:2.
(2) redox reaction prepares Ni nano wire.
The Ni nano wire liquid growth liquid prepared in step (1) is transferred in clean beaker, then it is sealed with preservative film, and on diaphragm seal, stay a little aperture.Being put into by beaker in constant temperature water bath apparatus, under the externally-applied magnetic field of 0.4 tesla, 70 degrees Celsius are reacted 1 hour.
(3) Ni nano wire simple substance is separated.
First Magnetic Isolation Ni nano wire: utilize Magnet to be transferred in clean container by the Ni nano wire of generation；Then Ni nano wire is cleaned: be respectively washed 3 times with deionized water, dehydrated alcohol；Finally being dried Ni nano wire: in vacuum drying oven, 60 degrees Celsius are dried 12 hours, i.e. prepare pure Ni nano wire simple substance.
A kind of NiO/Ni self-supported membrane, including described Ni nano wire and with the NiO/Ni composite of described Ni nano wire calcining prepared 1, in described NiO/Ni composite, Ni and NiO molar ratio is 10:1, and described NiO/Ni self-supported membrane thickness is 30 μm.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.Shown in its scanning electron microscope (SEM) photograph such as Fig. 5 (b).
Described NiO/Ni self-supported membrane, its preparation method, comprise the following steps:
A described Ni nano wire is dispersed in surfactant organic solution by ().
Described Ni nano wire is dispersed in the ethylene glycol solution of the polyvinylpyrrolidone that concentration is 1wt%, prepares Ni nanowire dispersion.Described Ni nano wire and organic solvent mass ratio are 1:2500.For making Ni nano wire dispersed, use the ultrasonic washing unit of 100 watts, to Ni nanowire dispersion ultrasonic disperse 10 minutes.
B Ni nanowire dispersion sucking filtration is prepared Ni self-supported membrane by ().
The Ni nanowire dispersion that will prepare in step (a), the method using sucking filtration, transfer on microporous filter membrane.Repeatedly clean the Ni self-supported membrane on microporous filter membrane with deionized water, be then vacuum dried 5 hours with 60 degrees Celsius of vacuum drying oven, after stripping, i.e. prepare Ni self-supported membrane.
C () oxygen-containing atmosphere is calcined Ni self-supported membrane prepare NiO/Ni self-supported membrane.
The Ni self-supported membrane prepared in step (b) is calcined in air atmosphere, calcining heat 400 degrees Celsius, calcining annealing time 10 minutes, i.e. prepare NiO/Ni self-supported membrane.
Described NiO/Ni self-supported membrane, has good pliability.Being verified by experiments, described NiO/Ni self-supported membrane has good capacitive property, as shown in figure 11, can be used as the active substance of super capacitor
Those skilled in the art is easy to understand; the foregoing is only presently preferred embodiments of the present invention; not in order to limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, should be included within the scope of the present invention.
Claims (8)
1. the preparation method of a NiO/Ni self-supported membrane, it is characterised in that comprise the following steps:
A Ni nano wire is dispersed in surfactant organic solution by (), form Ni nano wire
Dispersion liquid；
Described Ni nano wire average diameter is between 200nm to 300nm, and average length is 50,000nm
Between 200,000nm；
B Ni nanowire dispersion that () will prepare in step (a), the method using sucking filtration, transfer
On microporous filter membrane, peel off after cleaning, drying and obtain Ni self-supported membrane；
C the Ni self-supported membrane prepared in step (b) is calcined in oxygenous atmosphere and is obtained NiO/Ni by ()
Self-supported membrane.
2. preparation method as claimed in claim 1, it is characterised in that the table described in step (a)
Face activating agent organic solution is the ethylene glycol solution of the polyvinylpyrrolidone of 1wt%, described Ni nano wire
With organic solution mass ratio is between 1:1000 to 1:2500, described process for dispersing uses 100 watts
Ultrasonic disperse 10 minutes.
3. preparation method as claimed in claim 1, it is characterised in that containing described in step (c)
Oxygen atmosphere is air atmosphere, calcining heat 350 degrees Celsius to 450 degrees Celsius, calcines annealing time 3
Minute to 10 minutes.
4. preparation method as claimed in claim 1, it is characterised in that
The preparation method of described Ni nano wire comprises the following steps:
(1) configuration Ni nano wire liquid growth liquid: using Ni salt as presoma, be dissolved in organic molten
In agent, prepare Ni precursor solution；Organic reducing agent is dissolved in described organic solvent, prepares also
Former agent solution；Ni precursor solution is slowly scattered in strong basicity organic solvent, adds reducing agent
Solution, is eventually adding surfactant organic solution, prepares Ni nano wire liquid growth liquid；
(2) under externally-applied magnetic field, Ni nano wire liquid growth liquid generation redox reaction is made, system
Standby Ni nano wire simple substance；
(3) Magnetic Isolation clean Ni nano wire simple substance, dried prepares as claimed in claim 1
Ni nano wire.
5. preparation method as claimed in claim 4, it is characterised in that the Ni described in step (1)
Salt 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%；
Described strong basicity organic solvent is the sodium hydroxide ethylene glycol solution of 1.5mol/L；Described surfactant
Organic solution is the polyvinylpyrrolidone of 2wt%；Described Ni precursor solution, strong basicity organic solution,
The mixed proportion of reducing agent organic solution is volume ratio 1:4:2.
6. preparation method as claimed in claim 4, it is characterised in that the oxygen described in step (2)
Changing reduction reaction conditions is 70 degrees Celsius of constant temperature, and the response time is 1 hour, described applied field strengths
It it is 0.4 tesla.
7. a NiO/Ni self-supported membrane, it is characterised in that according to as any in claim 1 to 6
One described method prepares.
8. the application of a NiO/Ni self-supported membrane as claimed in claim 7, it is characterised in that
It is used as the active substance of super capacitor.
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| CN106541145A (en) * | 2016-10-28 | 2017-03-29 | 四川大学 | A kind of graphene oxide magnetic metal nanowire composite and preparation method thereof |
| CN108330505B (en) * | 2018-02-28 | 2020-07-28 | 中国科学院上海高等研究院 | Catalyst for electrocatalytic oxidation of methane and preparation method and application thereof |
| 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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