CN107240507A - A kind of nanoporous nickel nickel electrode material for super capacitor and preparation method thereof - Google Patents
A kind of nanoporous nickel nickel electrode material for super capacitor and preparation method thereof Download PDFInfo
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- CN107240507A CN107240507A CN201710583968.5A CN201710583968A CN107240507A CN 107240507 A CN107240507 A CN 107240507A CN 201710583968 A CN201710583968 A CN 201710583968A CN 107240507 A CN107240507 A CN 107240507A
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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
- H01G11/46—Metal oxides
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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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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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
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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 present invention is a kind of nanoporous nickel nickel electrode material for super capacitor and preparation method thereof.The electrode material is made up of collector with active material.Collector is the natural complex of ni-based amorphous alloy and nanoporous nickel, and wherein ni-based amorphous alloy is as intermediate core layer, and both sides are nanoporous nickel dam；Bar-shaped nickel oxide is dispersed in nanoporous nickel surface as active material, and the hexagonal prism shape of rule is presented in bar-shaped nickel oxide, and rod length is 1~2 μm, a diameter of 0.1~0.3 μm；Described Ni Ti Zr Al ni-based amorphous alloy composition is Ni40+x(Ti0.35Zr0.45Al0.20)60‑x(x=0~5).The present invention to be to aoxidize the bar-shaped nickel oxide of method acquisition that immersion is combined with heat treatment, it is to avoid the use of organic reagent in preparation process, saves the energy；Relatively complicated chemical means are eliminated, the complexity of equipment is reduced, hence it is evident that shorten the production cycle, is easy to large-scale production.
Description
Technical field：
The invention belongs to capacitor electrode material invention field, more particularly to a kind of super electricity of nanoporous nickel nickel
Container electrode material and preparation method thereof.
Background technology：
In recent years, due to the growth of population and developing rapidly for World Economics, the environmental pollution of facing mankind and the energy
Shortage problem is increasingly severe.Simultaneously as fossil fuel is non-renewable, a kind of sustainable use is developed, environment-friendly
New type of energy storage device it is extremely urgent.Ultracapacitor has power density height, charging interval short, service life length etc. excellent
Put and be widely used in the fields such as electric automobile, military affairs, mobile communication equipment, so as to cause the extensive pass of researcher
Note.
Ultracapacitor is also known as electrochemical capacitor, is divided into two kinds according to energy storage mechnism：One class is made using carbon-based material
The double layer capacitor of electrode；Another kind of is the main faraday's standard/fake capacitance for making electrode using metal oxide.Carbon material because
It has excellent heat conduction and electric conductivity, and heat endurance is good, and surface area is high, and pore passage structure is controllable, extensive the advantages of cheap
For in double layer capacitor, but relatively low specific capacitance value seriously limits the development of carbon material industrially.Relative to carbon
Material, metal oxide is as the electrode material of ultracapacitor, and its specific capacitance value has greatly improved.Ruthenium-oxide (RuO2)
It is a kind of ideal metal oxide electrode material, its specific capacitance is up to 768F/g.But ruthenium-oxide belongs to noble metal
Resource, expensive, more applied to military industry field, therefore research worker endeavours to find with cheap metal oxide.Oxidation
Nickel (NiO), manganese dioxide (MnO2) etc. transition metal oxide, they have and RuO2Similar property, and aboundresources, valency
Lattice are cheap, are expected to the electrode alternative materials as ultracapacitor.Wherein, nickel oxide (NiO) is due to environment-friendly, cost
It is low, the advantages of surface and controllable structural behaviour, the ideal electrode material of practical application can be most met as a kind of.
However, NiO is as electrode material application, there is also some drawbacks.NiO is a kind of semi-conducting material, generally by changing
Learn liquid phase, vapour deposition process to prepare, obtained oxide self-conductive is poor, nano particle easily occurs to reunite and cause its electric capacity
Characteristic declines, and cycle life is undesirable, and which greatly limits its practical application.Meanwhile, the NiO of powder morphology
Can not the independent electrode as ultracapacitor, it is necessary to depend on and be pressed into electrode slice on carrier (also known as collector) and can send out
Its capacitance characteristic is waved, not only in collector, conductive increasing in the electrode for nano-active material being assembled into using traditional rubbing method
Strong agent, the inside of binding agent and active material and interface introduce a large amount of electric charge transmission resistance, and can not efficiently solve work
The problem of utilization rate of property material is relatively low.Therefore develop a kind of chemical property to protrude, structure-integrated degree is high and prepares work
The simple combination electrode material of skill turns into the emphasis in front electrode investigation of materials field.
First technology, a kind of publication number CN102874884A " preparation side of electrode material for super capacitor nickel oxide
In method ", the patent, the step of preparing porous flower-shaped nickel oxide includes：It is molten with Nickelous nitrate hexahydrate and polyvinylpyrrolidone PVP
Mixed solution is made in the mixed solution stirring of formaldehyde and water in solution, and mixed solution is poured into hydrothermal reaction kettle after stirring,
Reaction 3-24 hours under 150-200 DEG C of hydrothermal condition, then both obtain electrode of super capacitor material through cooling, centrifugation, dry and calcining
Material.Porous flower-shape Ni O electrode materials prepared by this method have higher specific capacitance and good electrochemical stability, but methanol concurrently
It is volatile, react easily produce danger at high temperature, security is low；And preparation process is cumbersome time-consuming, cost is higher, its industry
Change degree is low.Meanwhile, the patent merely provides a kind of NiO preparation method, it is impossible to be applied directly in ultracapacitor, still
Need follow-up electrode slice preparation process.
First technology, a kind of publication number CN104332328A " super electricity of nickel oxide/polyaniline using nickel foam as substrate
Porous nickel foam is pre-processed in the preparation method of container electrode material ", the patent, the collector of electrode is used as；It
Afterwards with conductive polymer polyanilinc as electrode intermediate layer, the growth in situ polyaniline nano-rod in foam nickel base；Final electricity
Chemical deposition nickel oxide nano piece active layer, obtains a kind of with high-specific surface area, the electrode material for super capacitor of high activity.
The patent prepares polyaniline and nickel oxide active layer, this exogenous composite square using chemical/electrochemical deposition process
Formula make it that the adhesion between different structure layer is poor, and conducting polymer (polyaniline) is stable during long-term recycling
Property is poor, and nickel oxide active layer is easy to fall off.
First technology, publication number CN104269279B " a kind of ultracapacitor self-supporting compound electric pole piece and its preparation
In method ", the patent, a kind of nanoporous nickel/oxygen of self-supporting has been prepared by " de- alloy-autoxidation " one-step method
Change nickel combination electrode material.The preparation technology is simple, easily operation, but the active material nano-nickel oxide bag of the electrode material
The nanoporous nickel ligament generation on surface is covered, its content is smaller, therefore chemical property is not protruded；The oxidation obtained simultaneously
Nickel has no obvious crystal structure, therefore is regulated and controled also more difficult to the amount of nickel oxide.
The content of the invention：
The purpose of the present invention is to overcome to deposit in the nickel oxide combination electrode material preparation method for be currently used in ultracapacitor
Deficiency, while the chemical property for improving nickel oxide electrode material is received there is provided a kind of simple preparation efficient, with low cost
The method of meter Duo Kong nickel nickel combination electrode materials.Pass through short time, the de- alloy treatment of high concentration corrosive liquid in the present invention
(selective corrosion) prepares nanoporous nickel, and then nanoporous nickel is entered with being heat-treated the method being combined using oxidation immersion
Row processing, prepares the nickel oxide with rhabdolith form first.The nanoporous nickel nickel that the present invention is prepared is
It is a kind of to prepare completion simultaneously from collector electrode material, active material and collector, answered compared to nickel oxide prepared by sedimentation
Composite electrode material has bigger specific surface area, and nickel oxide is difficult to come off from collector.As electrode material for super capacitor,
With excellent chemical property, it is used alone at the same time as self-support type electrode slice.
The technical scheme is that：
A kind of nanoporous nickel nickel electrode material for super capacitor, described electrode material is by collector and activity
Material composition.Collector is the natural complex of ni-based amorphous alloy and nanoporous nickel, and wherein ni-based amorphous alloy is in
Between sandwich layer, both sides be nanoporous nickel dam；Bar-shaped nickel oxide is dispersed in nanoporous nickel surface, bar-shaped oxygen as active material
Change the hexagonal prism shape that rule is presented in nickel, rod length is 1~2 μm, a diameter of 0.1~0.3 μm；
Described ni-based amorphous alloy composition is Ni40+x(Ti0.35Zr0.45Al0.20)60-x(x=0~5)；Wherein, in alloy
Index number is each element atomic percentage；
The preparation method of described nanoporous nickel nickel electrode material for super capacitor, comprises the following steps：
The first step, prepares Ni-Ti-Zr-Al presoma AMORPHOUS ALLOY RIBBONSs
According to the atomic percent of each element in subject alloy, pure Ni, pure Ti, pure Zr, the common 20g of pure Al are taken, after mixing
Alloy raw material be placed in vacuum arc furnace ignition, melting electric current is 50~120A, and Ni-Ti-Zr-Al alloy cast ingots are made；In vacuum
Get rid of with the alloy cast ingot of acquisition is heated into molten condition in machine, aluminium alloy is quickly blown out using inert gas, makes melting
Liquid metal rapid solidification on the copper roller of high speed rotation, prepares thick 40~50 μm, width 2cm AMORPHOUS ALLOY RIBBONS；
Described alloying component is Ni40+x(Ti0.35Zr0.45Al0.20)60-x(x=0~5)；Wherein, index number in alloy
For each element atomic percentage；
Described vacuum gets rid of carrying device preparation condition：Vacuum is 9.0 × 10-4Pa；Pressure needed for blowing casting is 0.1MPa；
Copper roller rotating speed needed for blowing casting is 34-36m/s；
Second step, de- alloy prepares nanoporous nickel
Above-mentioned alloy strip is placed in acid solution 20~60min of immersion at room temperature, by the band after de- alloy spend from
Sub- water cleaning；
Described acid solution is hydrofluoric acid, and solution concentration is 0.4~0.6M；
3rd step, oxidation immersion-heat treatment prepares bar-shaped nickel oxide
Nanoporous nickel made from second step is placed in 4~8h of immersion in mixed solution, deionized water rinsing is used after taking-up
Afterwards, it is placed in heat-treatment furnace and carries out 0.5~1.5h of heat treatment, temperature is set as 210~250 DEG C；Nanometer is obtained after heat treatment many
Hole nickel nickel electrode material for super capacitor, is placed in vacuum drying chamber and preserves.
Described mixed solution is KOH solution and H2O2Solution is mixed, and KOH concentration is 1~2mol/L, H2O2Concentration
For 30wt.%, mixed volume ratio is KOH solution:H2O2Solution=2:1.
Described Ni, Ti, Zr, Al purity is 99.9wt.%.
Described inert gas is the high-purity argon gas of purity 99.99%.
The preparation method of above-mentioned nanoporous nickel nickel electrode material for super capacitor, raw material used and equipment
Obtained by known approach, operating procedure used is that those skilled in the art can grasp.
Compared with prior art, the substantive distinguishing features of the protrusion of the inventive method are as follows：
First, nickel oxide common in the art is more with nano particle (including nanometer sheet, nano wire and nanocluster)
Or oxide-film form is combined with collector, the bar-shaped nickel oxide prepared in the present invention is regular hexagonal prism shape, this
Planting crystal morphology has novelty；Second, compound electric of the combination compared to film/layer shape of nanoporous nickel and bar-shaped nickel oxide
Pole material has bigger specific surface area, while the content with regular Rod-like shape nickel oxide is easier to regulation and control；3rd, this hair
Obtained nickel oxide dispersiveness is aoxidized in bright by carrier of nanoporous nickel more preferably, is not susceptible to reunite, simultaneous oxidation nickel is with receiving
Combination between rice porous nickel is all right, and both are combined naturally, therefore nickel oxide is difficult for drop-off, are using electrode material
There is good property retention rate and longer cycle life in journey.
In preparation method, substantive distinguishing features one of the invention are to prepare nano-nickel oxide relative to hydro-thermal method and sedimentation
The preparation method that alloy combination oxidation immersion-heat treatment is taken off in combination electrode material, the present invention is undoubtedly simpler, is easy to behaviour
Make, and without the operation such as sealing, HTHP, save the energy and labour；Second, the selection of oxidation immersion mixed liquor has more
Targetedly, the addition of nickel salt is had no, nickel oxide is obtained in autoxidizable mode；Meanwhile, H2O2Addition provide one it is oxygen-enriched
Environment, the method that the electroxidation in alkaline solution is instead of with natural immersion, the heat treatment under specified temp is combined, into
The nickel that realizes of work(generates nickel hydroxide, then is changed into the process of bar-shaped nickel oxide；3rd, it is heat-treated and prior art
CN103553151B calcining is compared, and treatment temperature is lower, and the time is shorter, and the energy is saved while nickel oxide generation is ensured
And shorten and prepare duration.
The invention has the advantages that：
(1) method that the present invention is combined with aoxidizing immersion with being heat-treated first obtains bar-shaped nickel oxide, compared to existing skill
The methods such as the hydro-thermal method generally used in art prepare nano-nickel oxide, and (solution that current techniques are used typically contains nickel salt, uses
Hydro-thermal, chemical precipitation, the method such as electrochemical deposition obtains nickel oxide, calcines 30~200 points under 300~500 degrees Celsius afterwards
Clock), it is to avoid the use of organic reagent in preparation process, save the energy；Relatively complicated chemical means are eliminated, are reduced
The complexity of equipment, hence it is evident that shorten the production cycle, is easy to large-scale production.
(2) bar-shaped nickel oxide is generated in nanoporous nickel sheet surface oxidation in the present invention, there is gap between nickel oxide rod
And be uniformly dispersed in nanoporous nickel surface, compared with prior art in layered composite structure, the present invention in electrode material
With bigger specific surface area and porosity, it is possible to increase the transmission rate of electrolyte intermediate ion, active material is preferably played
Capacitance characteristic.
(3) compared to publication number CN104269278A " a kind of self-supporting nanoporous nickel nickel compound electric pole piece and its
Preparation method ", the present invention creatively adds oxidation immersion-heat treatment on the basis of de- alloy prepares nanoporous nickel
Method, prepares the nickel oxide with rhabdolith form, its activity substance content increase, while can be joined by adjusting process
Number regulates and controls the content and form of nickel oxide to a certain extent.Its optimal specific capacitance value is up to 1504.8F/cm3(based on electrode slice
Overall volume), use one-step method to take off the nanoporous nickel electrode material prepared by alloy better than in first technology.
Brief description of the drawings：
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is the microscopic structure stereoscan photograph of obtained nickel sheet/nickel oxide in embodiment 1.
Fig. 2 is the energy spectrum analysis figure in the stereoscan photograph of obtained nickel sheet/nickel oxide in embodiment 1.
Fig. 3 is the stereoscan photograph under obtained bar-shaped nickel oxide high power in embodiment 1.
Fig. 4 is the X ray diffracting spectrum of obtained nickel sheet/nickel oxide in embodiment 1.
Fig. 5 is the cyclic voltammetry curve figure of obtained nickel sheet/nickel oxide in embodiment 1.
Fig. 6 is the microscopic structure stereoscan photograph of obtained nickel sheet/nickel oxide in embodiment 2.
Fig. 7 is the microscopic structure stereoscan photograph of obtained nickel sheet/nickel oxide in embodiment 3.
Embodiment
Embodiment 1：
The first step, prepares presoma alloy
According to subject alloy Ni45(Ti0.35Zr0.45Al0.20)55The atomic percent of middle each element, weighs mass fraction equal
Female conjunction is mixed to get for 99.9wt.% pure Ni 8.635g, pure Ti rods 3.013g, pure Zr rods 7.382g, pure Al pieces 0.970g
The raw metal mixed, is then placed in vacuum arc furnace ignition by golden raw material 20g, and 20g purity is only for 99.9wt.% pure titanium
It is placed in vacuum arc furnace ignition and is not contacted with foundry alloy raw material, is used as oxygen scavenging material melting；Under argon gas protection, melting 4 is repeated
Secondary foundry alloy, 40 seconds or so every time, to ensure alloy structure uniformity；Cool to room temperature after the completion of melting with the furnace, you can obtain
Ni45(Ti0.35Zr0.45Al0.20)55Alloy cast ingot (foundry alloy).
By the foundry alloy obtained after melting remove surface scale and be cut into it is suitably sized after be placed in quartz ampoule, profit
Band machine is got rid of with vacuum and prepares amorphous alloy ribbon, preparation condition is：Vacuum 9.0 × 10-4Pa, blows casting pressure 0.1MPa, copper
Roller rotating speed is 34m/s.Foundry alloy is placed in quartz ampoule, and molten state is heated under the protective atmosphere of argon gas and blows cast into amorphous conjunction
Gold bar band, prepares thick 50 μm, width 2cm alloy strip；
Second step, de- alloy prepares nanoporous nickel
5cm is taken from above-mentioned alloy strip, is placed at room temperature in 0.6M hydrofluoric acid corrosive liquids and carries out de- alloy treatment
40min, then rinses sample 3 times repeatedly with deionized water；
3rd step, oxidation immersion-heat treatment prepares bar-shaped nickel oxide
Nanoporous nickel bar band obtained above is placed in KOH and H2O2Soak 8h in mixed liquor, the mixed liquor by
2mol/L KOH 40ml and 30wt.%H2O220ml is constituted；After immersion is finished, sample deionized water rinsing 3 times is taken out, is placed in
Temperature is carries out heat treatment 1h in 220 DEG C of heat-treatment furnace, it is 1.0 × 10 that sample is put into vacuum by heat treatment after terminating-1MPa
Preserved in vacuum drying chamber.
, will be obtained above in order to detect the chemical property of the nanoporous nickel nickel electrode material prepared
Electrode for super capacitor material carries out cyclic voltammetry in 1mol/LKOH solution, and test uses CHI660e electrochemistry works
Stand, three-electrode system, nanoporous nickel nickel obtained above is working electrode, and gauze platinum electrode is auxiliary electrode, Ag/
AgCl electrodes are reference electrode, and sweep speed is 10mV/s, and voltage range scope is 0~0.5V.
Fig. 1 is prepared bar-shaped oxidation in the microscopic structure stereoscan photograph of nanoporous nickel nickel, this example
Nickel is uniform, dense growth in nanoporous nickel surface, 2 μm of the length of bar-shaped nickel oxide, the diameter of rod is about 0.3 μm.Simultaneously can
To find out, bar-shaped nickel oxide is along the direction preferential growth perpendicular to collection liquid surface, and bar-shaped nickel oxide is in nickel sheet in region
Coverage rate reaches 100% (area accounting).
Fig. 2 is the pattern photo of bar-shaped nickel oxide under high power, can be clearly observed bar-shaped nickel oxide and rule is presented
Hexagonal prism shape.
Fig. 3 is the energy spectrum analysis figure in the stereoscan photograph of nanoporous nickel nickel, shows rod made from this example
The main component of shape structure organization is nickel and oxygen, and nickel and oxygen percentage close to 1:1, it is oxidation to show the club shaped structure of generation
Nickel.Minimal amount of Zr elements, Ti elements and Al elements are present in power spectrum result, show Zr, Ti, Al element on band top layer de-
It is selectively dissolved substantially in alloy process.
Fig. 4 is to obtained nanoporous nickel nickel in the X ray diffracting spectrum of nanoporous nickel, the present embodiment
Phase composition carries out X-ray diffractogram analysis of spectrum, shows that material made from this example is made up of elemental nickel and nickel oxide, illustrates original
Ti elements, Zr elements, Al elements in alloy strip are corroded and removed by selectivity, and success is prepared on nanoporous nickel
To bar-shaped nickel oxide.
The CV curves that Fig. 5 nanoporous nickel nickel combination electrode materials made from the present embodiment are measured are (by making
Measured with CHI660e electrochemical workstations).Material specific capacitance value is characterized with the area of curve enclosed region, is computed comparing
Capacitance is 1504.8F/cm3, the 847.9F/cm obtained than first technology CN104269278A377.5% is improved, is shown very
Prominent specific capacitance characteristic.
Embodiment 2：
The first step, prepares presoma alloy
According to subject alloy Ni42.5(Ti0.35Zr0.45Al0.20)57.5The atomic percent of middle each element, weighs mass fraction
Pure Ni 8.140g, pure Ti rods 3.144g, pure Zr rods 7.703g, the pure Al pieces 1.103g for being 99.9wt.% are mixed to get mother
The raw metal mixed, is then placed in vacuum arc furnace ignition by alloy raw material 20g, by the pure titanium that 20g purity is 99.9wt.%
Independently it is placed in vacuum arc furnace ignition and is not contacted with foundry alloy raw material, is used as oxygen scavenging material melting；Under argon gas protection, melting is repeated
4 foundry alloys, 40 seconds or so every time, to ensure alloy structure uniformity；Cool to room temperature after the completion of melting with the furnace, you can obtain
Ni42.5(Ti0.35Zr0.45Al0.20)57.5Alloy cast ingot (foundry alloy).
By the foundry alloy obtained after melting remove surface scale and be cut into it is suitably sized after be placed in quartz ampoule, profit
Band machine is got rid of with vacuum and prepares amorphous alloy ribbon, preparation condition is：Vacuum 9.0 × 10-4Pa, blows casting pressure 0.1MPa, copper
Roller rotating speed is 35m/s.Foundry alloy is placed in quartz ampoule, and molten state is heated under the protective atmosphere of argon gas and blows cast into amorphous conjunction
Gold bar band, prepares thick 47 μm, width 2cm alloy strip；
Second step, de- alloy prepares nanoporous nickel
5cm is taken from above-mentioned alloy strip, is placed at room temperature in 0.5M hydrofluoric acid corrosive liquids and carries out de- alloy treatment
60min, then rinses sample 3 times repeatedly with deionized water；
3rd step, oxidation immersion-heat treatment prepares bar-shaped nickel oxide
Nanoporous nickel bar band obtained above is placed in KOH and H2O2Soak 6h in mixed liquor, the mixed liquor by
1.5mol/LKOH 40ml and 30wt.%H2O220ml is constituted；After immersion is finished, sample deionized water rinsing 3 times is taken out, is put
Heat treatment 1h is carried out in temperature is 250 DEG C of heat-treatment furnace, it is 1.0 × 10 that sample is put into vacuum by heat treatment after terminating- 1Preserved in MPa vacuum drying chambers.
Fig. 6 is the microscopic structure stereoscan photograph of nickel sheet/nickel oxide, it is seen that when reduction de- alloy time and oxidation immersion
Between after, the growing amount of bar-shaped nickel oxide has been reduced, but still maintains continuous, uniform shape characteristic, the μ of nickel oxide rod length 1
M, a diameter of 0.3 μm of rod.Cyclic voltammetric survey is carried out to the nanoporous nickel nickel electrode material prepared in the present embodiment
Examination, condition and parameter be the same as Example 1, be computed specific capacitance value is 1418.4F/cm3, obtained than first technology CN104269278A
847.9F/cm3Improve 67.3%.Decreased compared to embodiment 1, this shows that the content of nickel oxide directly affects with distribution
The specific capacitance value of nanoporous nickel nickel electrode material.
Embodiment 3：
The first step, prepares presoma alloy
According to Ni in subject alloy40(Ti0.35Zr0.45Al0.20)60The atomic percent of each element, weighs mass fraction equal
Female conjunction is mixed to get for 99.9wt.% pure Ni 7.647g, pure Ti rods 3.275g, pure Zr rods 8.023g, pure Al pieces 1.055g
The raw metal mixed, is then placed in vacuum arc furnace ignition by golden raw material 20g, and 20g purity is only for 99.9wt.% pure titanium
It is placed in vacuum arc furnace ignition and is not contacted with foundry alloy raw material, is used as oxygen scavenging material melting；Under argon gas protection, melting 4 is repeated
Secondary foundry alloy, 40 seconds or so every time, to ensure alloy structure uniformity；Cool to room temperature after the completion of melting with the furnace, you can obtain
Ni40(Ti0.35Zr0.45Al0.20)60Alloy cast ingot (foundry alloy).
By the foundry alloy obtained after melting remove surface scale and be cut into it is suitably sized after be placed in quartz ampoule, profit
Band machine is got rid of with vacuum and prepares amorphous alloy ribbon, preparation condition is：Vacuum 9.0 × 10-4Pa, blows casting pressure 0.1MPa, copper
Roller rotating speed is 36m/s.Foundry alloy is placed in quartz ampoule, and molten state is heated under the protective atmosphere of argon gas and blows cast into amorphous conjunction
Gold bar band, prepares thick 42 μm, width 2cm alloy strip；
Second step, de- alloy prepares nanoporous nickel
5cm is taken from above-mentioned alloy strip, progress removal alloying processing in 0.4M hydrofluoric acid corrosive liquids is placed at room temperature
30min, then rinses sample 3 times repeatedly with deionized water；
3rd step, oxidation immersion-heat treatment prepares bar-shaped nickel oxide
Nanoporous nickel bar band obtained above is placed in KOH and H2O2Soak 4h in mixed liquor, the mixed liquor by
1mol/L KOH 40ml and 30wt.%H2O220ml is constituted；After immersion is finished, sample deionized water rinsing 3 times is taken out, is placed in
Temperature is carries out heat treatment 1h in 210 DEG C of heat-treatment furnace, it is 1.0 × 10 that sample is put into vacuum by heat treatment after terminating-1MPa
Vacuum drying chamber in preserve.
The microscopic structure stereoscan photograph of obtained nanoporous nickel nickel, bar-shaped nickel oxide in Fig. 7 the present embodiment
Growing amount significantly reduce, region inner area coverage rate is about 80%, nickel oxide rod in cluster-shaped assemble growth, 1 μm of length, directly
About 0.2 μm of footpath.Cyclic voltammetry, test-strips are carried out to the nanoporous nickel nickel electrode material prepared in the present embodiment
Part and parameter be the same as Example 1, be computed specific capacitance value is 1167.6F/cm3, obtained than first technology CN104269278A
847.9F/cm3Improve 37.8%.
Comparative example 1
Hydrofluoric acid solution concentration selection used in de- alloy is 0.3M, and other conditions be the same as Example 1 takes off sample surfaces after alloy
Uniform nano-porous structure is not formed, sample surfaces are generated without bar-shaped nickel oxide after simultaneous oxidation immersion-heat treatment.
Comparative example 2
After de- alloy, sample is in KOH and H2O22h is soaked in mixed liquor, as a result other conditions be the same as Example 1 shows：Nanometer
Porous nickel surface only has the bar-shaped nickel oxide of the small size (length is less than 1 μm) of the few scattered distribution of quantity, prepares
Nanoporous nickel nickel combination electrode material specific capacitance value is only 237.1F/cm3。
Comparative example 3
By KOH and H2O2KOH solution concentration is reduced to 0.5mol/L in mixed liquor, and as a result other conditions be the same as Example 1 shows
Show：Nanoporous nickel surface is generated without bar-shaped nickel oxide.
Comparative example 4
KOH solution and H are replaced with 2mol/L NaOH solution2O2As a result mixing, other conditions be the same as Example 1 shows, receives
Rice porous nickel surface does not generate bar-shaped nickel oxide.
Comparative example 5
Subject alloy is from the Ni-Ti-Zr-Al alloys that nickel element content is 35at.%, other conditions be the same as Example 2, hair
The alloy strip poor mechanical property now prepared, fragility is larger.Taken off in 0.5M HF after alloy 60min, sample etches are crushed
Into small, it is impossible to maintain the mechanical integrity of initial cut.
Above comparative example 1-5 is the case of the failure of an experiment, illustrates that arbitrarily changing preparation parameter of the present invention will be unable to success
Obtain a great deal of, equally distributed bar-shaped nickel oxide, thus nanoporous nickel/oxygen of electrochemical performance can not be prepared
Change nickel electrode for super capacitor material.
Above example and comparative example show, the nanoporous nickel nickel electrode for super capacitor material in the present invention
The preparation method of material is arrived by substantial amounts of experiment and labour income, by continuously attempting to, and constantly gropes just to draw optimal
Process conditions.The parameter of each process procedure is only strictly controlled, the nanoporous of electrochemical performance could be successfully obtained
Nickel nickel electrode material.
Unaccomplished matter of the present invention is known technology.
Claims (3)
1. a kind of nanoporous nickel nickel electrode material for super capacitor, it is characterized in that described electrode material includes afflux
Body and active material；Collector is the natural complex of ni-based amorphous alloy and nanoporous nickel, and wherein ni-based amorphous alloy is made
For intermediate core layer, both sides are nanoporous nickel dam；Bar-shaped nickel oxide is dispersed in nanoporous nickel surface, rod as active material
The hexagonal prism shape of rule is presented in shape nickel oxide, and rod length is 1 ~ 2 μm, a diameter of 0.1 ~ 0.3 μm；
Described ni-based amorphous alloy composition is Ni40+x(Ti0.35Zr0.45Al0.20)60-x(x=0~5)；Wherein, subscript number in alloy
Word is each element atomic percentage；
Described nanoporous nickel nickel electrode material for super capacitor is made by lower section method, is comprised the following steps：
The first step, prepares Ni-Ti-Zr-Al presoma AMORPHOUS ALLOY RIBBONSs
According to the atomic percent of each element in subject alloy, pure Ni, pure Ti, pure Zr, pure Al totally 20 g are taken, is closed mixed
Golden raw material is placed in vacuum arc furnace ignition, and melting electric current is 50 ~ 120 A, and Ni-Ti-Zr-Al alloy cast ingots are made；Band is got rid of in vacuum
The alloy cast ingot of acquisition is heated to molten condition in machine, aluminium alloy is quickly blown out using inert gas, makes the liquid of melting
Metal rapid solidification on the copper roller of high speed rotation, prepares thick 40 ~ 50 μm, wide 2 cm AMORPHOUS ALLOY RIBBONS, described conjunction
Golden composition is：Ni40+x(Ti0.35Zr0.45Al0.20)60-x(x=0~5)；Wherein, index number is each element atomic percent in alloy
Number；
Described vacuum gets rid of carrying device preparation condition：Vacuum is 9.0 × 10-4 Pa；Pressure needed for blowing casting is 0.1MPa；Blow
Copper roller rotating speed needed for casting is 34-36 m/s；
Second step, de- alloy prepares nanoporous nickel
Above-mentioned alloy strip is placed in 20 ~ 60 min of immersion in acid solution at room temperature, by the band deionized water after de- alloy
Cleaning；
Described acid solution is hydrofluoric acid, and solution concentration is 0.4 ~ 0.6 M;
3rd step, oxidation immersion-heat treatment prepares bar-shaped nickel oxide
Nanoporous nickel made from second step is placed in 4 ~ 8 h of immersion in mixed solution, with after deionized water rinsing after taking-up, put
0.5 ~ 1.5 h of heat treatment is carried out in heat-treatment furnace, temperature is set as 210 ~ 250 DEG C, nanoporous nickel/oxygen is obtained after heat treatment
Change nickel electrode material for super capacitor；
Described mixed solution is KOH solution and H2O2Solution is mixed, and KOH concentration is 1 ~ 2 mol/L, H2O2Concentration is 30
Wt.%, mixed volume ratio is KOH solution:H2O2 Solution=2:1.
2. the preparation method of nanoporous nickel nickel electrode material for super capacitor as claimed in claim 1, it is characterized in that
Described Ni, Ti, Zr, Al purity is 99.9 wt.%.
3. the preparation method of nanoporous nickel nickel electrode material for super capacitor as claimed in claim 1, it is characterized in that
Described inert gas is the high-purity argon gas of purity 99.99%.
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| CN108054022A (en) * | 2017-12-07 | 2018-05-18 | 安徽工业大学 | A kind of non-crystaline amorphous metal combination electrode of surface layer porous structure nickel cobalt oxide and preparation method thereof |
| CN108493000A (en) * | 2018-03-23 | 2018-09-04 | 中国科学院宁波材料技术与工程研究所 | A kind of flexible nano porous metals/oxide super capacitor electrode material and preparation method thereof |
| CN108707922A (en) * | 2018-05-03 | 2018-10-26 | 北京科技大学 | A kind of flexible nano is porous/amorphous composite material and preparation method thereof |
| CN109023412A (en) * | 2018-08-24 | 2018-12-18 | 北京科技大学 | A kind of nanoporous ambrose alloy/amorphous combination electrode material and preparation method thereof |
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| CN110379647A (en) * | 2019-08-14 | 2019-10-25 | 河北工业大学 | A kind of nanoporous nickel nickel loads the preparation method of ultra-thin cobalt hydroxide nanometer sheet flexible electrode material |
| CN110706939A (en) * | 2019-09-06 | 2020-01-17 | 暨南大学 | Nano porous nickel alloy/manganese dioxide electrode material and preparation method and application thereof |
| CN113416974A (en) * | 2021-03-22 | 2021-09-21 | 辽宁石油化工大学 | Method for rapidly preparing efficient porous silver electrocatalyst |
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| CN108054022A (en) * | 2017-12-07 | 2018-05-18 | 安徽工业大学 | A kind of non-crystaline amorphous metal combination electrode of surface layer porous structure nickel cobalt oxide and preparation method thereof |
| CN109935888A (en) * | 2017-12-19 | 2019-06-25 | 成都亦道科技合伙企业（有限合伙） | Current collector structure, lithium battery electric core and its lithium battery |
| CN108493000A (en) * | 2018-03-23 | 2018-09-04 | 中国科学院宁波材料技术与工程研究所 | A kind of flexible nano porous metals/oxide super capacitor electrode material and preparation method thereof |
| CN108707922A (en) * | 2018-05-03 | 2018-10-26 | 北京科技大学 | A kind of flexible nano is porous/amorphous composite material and preparation method thereof |
| CN109023412A (en) * | 2018-08-24 | 2018-12-18 | 北京科技大学 | A kind of nanoporous ambrose alloy/amorphous combination electrode material and preparation method thereof |
| CN110379647A (en) * | 2019-08-14 | 2019-10-25 | 河北工业大学 | A kind of nanoporous nickel nickel loads the preparation method of ultra-thin cobalt hydroxide nanometer sheet flexible electrode material |
| CN110379647B (en) * | 2019-08-14 | 2021-04-30 | 河北工业大学 | Preparation method of nano-porous nickel/nickel oxide loaded ultrathin cobalt hydroxide nanosheet flexible electrode material |
| CN110706939A (en) * | 2019-09-06 | 2020-01-17 | 暨南大学 | Nano porous nickel alloy/manganese dioxide electrode material and preparation method and application thereof |
| CN113416974A (en) * | 2021-03-22 | 2021-09-21 | 辽宁石油化工大学 | Method for rapidly preparing efficient porous silver electrocatalyst |
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