CN107240507B - 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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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 of collector and active material.Collector is the natural complex of ni-based amorphous alloy and nanoporous nickel, and wherein for ni-based amorphous alloy as intermediate core layer, two sides are nanoporous nickel layer；Rodlike nickel oxide is dispersed in nanoporous nickel surface as active material, and the hexagonal prism shape of rule is presented in rodlike nickel oxide, and stick length is 1~2 μm, and diameter is 0.1~0.3 μm；The Ni-Ti-Zr-Al ni-based amorphous alloy ingredient is Ni40+x(Ti0.35Zr0.45Al0.20)60‑x(x=0~5).The present invention obtains rodlike nickel oxide to aoxidize the method that immersion is combined with heat treatment, avoids 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 shortens the production cycle, is convenient for 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 technique:
In recent years, due to the growth of population and the rapid development of world economy, 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, environmental-friendly is developed
New type of energy storage device it is extremely urgent.Supercapacitor has power density height, charging time short, long service life etc. excellent
It puts and is widely used in the fields such as electric car, military affairs, mobile communication equipment, so as to cause the extensive pass of researcher
Note.
Supercapacitor is also known as electrochemical capacitor, and be divided into two kinds according to energy storage mechnism: one kind 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
The advantages that, with excellent thermally conductive and electric conductivity, thermal stability is good for it, and surface area is high, and cellular structure is controllable, cheap is extensive
For in double layer capacitor, but lower specific capacitance value seriously limits the development of carbon material industrially.Relative to carbon
Material, electrode material of the metal oxide as supercapacitor, specific capacitance value have greatly improved.Ruthenium-oxide (RuO2)
It is a kind of ideal metal oxide electrode material, specific capacitance is up to 768F/g.However ruthenium-oxide belongs to noble metal
Resource, it is expensive, it is applied to military industry field, therefore research worker endeavours to find cheap metal oxide more.Oxidation
Nickel (NiO), manganese dioxide (MnO2) etc. transition metal oxides, they have and RuO2Similar property, and resourceful, valence
Lattice are cheap, are expected to the electrode alternative materials as supercapacitor.Wherein, nickel oxide (NiO) is due to environmental-friendly, cost
It is low, the advantages that surface and controllable structural behaviour, become a kind of ideal electrode material for being most able to satisfy practical application.
However, NiO is as electrode material application, there is also some drawbacks.NiO is a kind of semiconductor material, usually by changing
Liquid phase, vapour deposition process preparation are learned, oxide self-conductive obtained is poor, and nano particle easily occurs to reunite and lead to its capacitor
Characteristic decline, and cycle life is undesirable, which greatly limits its practical applications.Meanwhile the NiO of powder morphology
It can not the independent electrode as supercapacitor, 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 binder and active material and interface introduce a large amount of charges and transmit resistance, and can not efficiently solve work
The relatively low problem of the utilization rate of property substance.Therefore it is prominent to develop a kind of chemical property, structure-integrated degree is high and prepares work
The simple combination electrode material of skill becomes the emphasis in front electrode investigation of materials field.
First technology, a kind of " preparation side of electrode material for super capacitor nickel oxide of publication number CN102874884A
Method ", in the patent, the step of preparing porous flower-shaped nickel oxide includes: molten with Nickelous nitrate hexahydrate and polyvinylpyrrolidone PVP
Solution stirs in the mixed solution of formaldehyde and water and mixed solution is made, and mixed solution is poured into hydrothermal reaction kettle after mixing evenly,
It is reacted 3-24 hours under 150-200 DEG C of hydrothermal condition, then both obtains electrode of super capacitor material through cooling, centrifugation, drying and calcining
Material.The porous flower-shape Ni O electrode material of this method preparation has both higher specific capacitance and good electrochemical stability, but methanol
Volatile, reaction is easy to produce danger at high temperature, and safety is low；And preparation process is cumbersome time-consuming, higher cost, industry
Change degree is low.Meanwhile the patent merely provides the preparation method of NiO a kind of, can be not applied directly in supercapacitor, still
Need subsequent electrode slice preparation process.
First technology, publication number CN104332328A's is " a kind of using nickel foam as the super electricity of the nickel oxide/polyaniline of substrate
The preparation method of container electrode material " pre-processes porous nickel foam in the patent, the collector as electrode；It
Use conductive polymer polyanilinc as electrode middle layer afterwards, 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 electrode material for super capacitor with high-specific surface area, high activity.
Polyaniline and nickel oxide active layer, this exogenous composite square is prepared using chemical/electrochemical deposition method in the patent
Formula makes the binding force between different structure layer poor, and conducting polymer (polyaniline) is stablized 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 supercapacitor self-supporting compound electric pole piece and its preparation
In the patent, a kind of nanoporous nickel/oxygen of self-supporting has been prepared by " de- alloy-autoxidation " one-step method for method "
Change nickel combination electrode material.The preparation process is simple, easy to operate, but the active material nano-nickel oxide packet of the electrode material
The nanoporous nickel ligament for covering surface generates, and content is smaller, therefore chemical property does not protrude；The oxidation obtained simultaneously
Nickel has no apparent crystal structure, therefore is regulated and controled to the amount of nickel oxide also more difficult.
Summary of the invention:
It is deposited in the nickel oxide combination electrode material preparation method for being currently used in supercapacitor the purpose of the present invention is overcoming
Deficiency, while improving the chemical property of nickel oxide electrode material, provide that one kind is simple and efficient, low-cost preparation is received
The method of meter Duo Kong nickel nickel combination electrode material.Pass through short time, the de- alloy treatment of high concentration corrosive liquid in the present invention
(selective corrosion) prepares nanoporous nickel, then using oxidation impregnate be heat-treated the method that combines to nanoporous nickel into
Row processing, prepares the nickel oxide with rhabdolith form for the first time.The nanoporous nickel nickel that the present invention is prepared is
One kind preparing completion from collector electrode material, active material and collector simultaneously, and the nickel oxide compared to sedimentation preparation is multiple
Composite electrode material has bigger specific surface area, and nickel oxide is not easy to fall 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 solution of the present invention is as follows:
A kind of nanoporous nickel nickel electrode material for super capacitor, the electrode material is by collector and activity
Material composition.Collector is the natural complex of ni-based amorphous alloy and nanoporous nickel, wherein in ni-based amorphous alloy conduct
Between sandwich layer, two sides be nanoporous nickel layer；Rodlike nickel oxide is dispersed in nanoporous nickel surface, rodlike oxygen as active material
Change the hexagonal prism shape that rule is presented in nickel, stick length is 1~2 μm, and diameter is 0.1~0.3 μm；
The ni-based amorphous alloy ingredient 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 the nanoporous nickel nickel electrode material for super capacitor, comprising the following steps:
The first step prepares Ni-Ti-Zr-Al presoma AMORPHOUS ALLOY RIBBONS
According to the atomic percent of each element in subject alloy, pure Ni, pure Ti, pure Zr, the total 20g of pure Al are taken, after mixing
Alloy raw material be placed in vacuum arc furnace ignition, melting electric current be 50~120A, be made Ni-Ti-Zr-Al alloy cast ingot；In vacuum
It gets rid of with the alloy cast ingot of acquisition is heated to molten condition in machine, is quickly blown out aluminium alloy using inert gas, make melting
Liquid metal quickly solidifies on high-speed rotating copper roller, prepares 40~50 μm thick, width 2cm AMORPHOUS ALLOY RIBBONS；
The alloying component is Ni40+x(Ti0.35Zr0.45Al0.20)60-x(x=0~5)；Wherein, index number in alloy
For each element atomic percentage；
The vacuum gets rid of carrying device preparation condition are as follows: vacuum degree is 9.0 × 10-4Pa；Pressure needed for blowing casting is 0.1MPa；
Copper roller revolving speed needed for blowing casting is 34-36m/s；
Second step, de- alloy prepare 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；
The acid solution is hydrofluoric acid, and solution concentration is 0.4~0.6M；
Third step, oxidation immersion-heat treatment prepare rodlike nickel oxide
Nanoporous nickel made from second step is placed in 4~8h of immersion in mixed solution, is rinsed after taking-up with deionized water
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；It is more that nanometer is obtained after heat treatment
Hole nickel nickel electrode material for super capacitor, places it in vacuum oven and saves.
The mixed solution is KOH solution and H2O2Solution mixes, and KOH concentration is 1~2mol/L, H2O2Concentration
For 30wt.%, mixed volume ratio is KOH solution: H2O2Solution=2:1.
The purity of described Ni, Ti, Zr, Al are 99.9wt.%.
The 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
It is obtained by well known approach, operating procedure used is that those skilled in the art can grasp.
Compared with prior art, the substantive distinguishing features outstanding of the method for the present invention are as follows:
Firstly, nickel oxide common in the art is mostly with nano particle (including nanometer sheet, nano wire and nanocluster)
Or oxidation film form, in conjunction with collector, the rodlike nickel oxide being prepared in the present invention is the hexagonal prism shape of rule, this
Kind crystal morphology has novelty；Second, the compound electric of the combination of nanoporous nickel and rodlike nickel oxide compared to film/layer shape
Pole material has bigger specific surface area, while there is the content of regular Rod-like shape nickel oxide to be easier to；Third, this hair
The nickel oxide dispersibility aoxidized in bright using nanoporous nickel as carrier is more preferable, is not susceptible to reunite, simultaneous oxidation nickel with receive
Combination between rice porous nickel is all right, and the two is naturally compound, therefore nickel oxide is not easily to fall off, is using electrode material
Conservation rate with good performance and longer cycle life in journey.
In preparation method, substantive distinguishing features of the invention are first is that prepare nano-nickel oxide relative to hydro-thermal method and sedimentation
Combination electrode material, the present invention in take off alloy combine oxidation immersion-heat treatment preparation method it is undoubtedly simpler, convenient for behaviour
Make, and without the operation such as sealing, high temperature and pressure, saves the energy and labour；Second, the selection that mixed liquor is impregnated in oxidation has more
Targetedly, the addition for having no nickel salt, obtains nickel oxide in a manner of autoxidizable；Meanwhile H2O2Addition provide one it is oxygen-enriched
Environment, with natural immersion instead of the method for the electroxidation in alkaline solution, the heat treatment under specific temperature is combined, at
The nickel that realizes of function generates nickel hydroxide, then is changed into the process of rodlike nickel oxide；Third, heat treatment and the prior art
The calcining of CN103553151B is compared, and treatment temperature is lower, and the time is shorter, saves the energy while guaranteeing that nickel oxide generates
And shorten preparation duration.
The invention has the following advantages:
(1) present invention obtains rodlike nickel oxide for the first time to aoxidize the method impregnated and combined with heat treatment, compares existing skill
The methods of hydro-thermal method generallyd use in art prepares nano-nickel oxide, and (solution that current techniques use typically contains nickel salt, uses
Hydro-thermal, chemical precipitation, the methods of electrochemical deposition obtain nickel oxide, calcine 30~200 points under 300~500 degrees Celsius later
Clock), the use of organic reagent in preparation process is avoided, the energy is saved；Relatively complicated chemical means are eliminated, are reduced
The complexity of equipment, hence it is evident that shorten the production cycle, be convenient for large-scale production.
(2) rodlike nickel oxide is generated in nanoporous nickel sheet surface oxidation in the present invention, and there are gaps between nickel oxide stick
And be uniformly dispersed in nanoporous nickel surface, layered composite structure compared to the prior art, the present invention in electrode material
With bigger specific surface area and porosity, the transmission rate of electrolyte intermediate ion can be improved, preferably performance active material
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 joined oxidation immersion-heat treatment on the basis of de- alloy prepares nanoporous nickel
Method prepares the nickel oxide with rhabdolith form, and activity substance content increases, while can join by adjusting technique
Number regulates and controls the content and form of nickel oxide to a certain extent.Its best specific capacitance value is up to 1504.8F/cm3(based on electrode slice
Overall volume), use one-step method to take off nanoporous nickel electrode material prepared by alloy better than in first technology.
Detailed description of the invention:
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is the microscopic structure stereoscan photograph of nickel sheet/nickel oxide obtained in embodiment 1.
Fig. 2 is the energy spectrum analysis figure in the stereoscan photograph of nickel sheet/nickel oxide obtained in embodiment 1.
Fig. 3 is the stereoscan photograph under rodlike nickel oxide high power obtained in embodiment 1.
Fig. 4 is the X ray diffracting spectrum of nickel sheet/nickel oxide obtained in embodiment 1.
Fig. 5 is the cyclic voltammetry curve figure of nickel sheet/nickel oxide obtained in embodiment 1.
Fig. 6 is the microscopic structure stereoscan photograph of nickel sheet/nickel oxide obtained in embodiment 2.
Fig. 7 is the microscopic structure stereoscan photograph of nickel sheet/nickel oxide obtained in embodiment 3.
Specific 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, it is equal to weigh mass fraction
Female conjunction is mixed to get for the pure Ni 8.635g of 99.9wt.%, pure Ti stick 3.013g, pure Zr stick 7.382g, pure Al piece 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 the pure titanium of 99.9wt.%
It is placed in vacuum arc furnace ignition and is not contacted with master alloy raw material, as oxygen scavenging material melting；Under protection of argon gas, melting 4 is repeated
Secondary master alloy, 40 seconds or so every time, to ensure alloy structure uniformity；Room temperature is cooled to the furnace after the completion of melting, can be obtained
Ni45(Ti0.35Zr0.45Al0.20)55Alloy cast ingot (master alloy).
By the master alloy obtained after melting remove surface scale and be cut into it is suitably sized be placed in quartz ampoule, benefit
Band machine is got rid of with vacuum and prepares amorphous alloy ribbon, preparation condition are as follows: vacuum degree 9.0 × 10-4Pa blows casting pressure 0.1MPa, copper
Roller revolving speed is 34m/s.Master alloy is placed in quartz ampoule, molten state is heated under the protective atmosphere of argon gas blows cast closing at amorphous
Gold bar band prepares 50 μm thick, width 2cm alloy strip；
Second step, de- alloy prepare nanoporous nickel
5cm is taken from above-mentioned alloy strip, is placed in 0.6M hydrofluoric acid corrosive liquid at room temperature and is carried out de- alloy treatment
40min, then by sample with deionized water repeated flushing 3 times；
Third step, oxidation immersion-heat treatment prepare rodlike nickel oxide
Nanoporous nickel bar band obtained above is placed in KOH and H2O2Impregnate 8h in mixed liquor, the mixed liquor by
2mol/L KOH 40ml and 30wt.%H2O220ml composition；After immersion, takes out sample and rinsed 3 times with deionized water, is placed in
Heat treatment 1h is carried out in the heat-treatment furnace that temperature is 220 DEG C, it is 1.0 × 10 that sample, which is put into vacuum degree, after heat treatment-1MPa
It is saved in vacuum oven.
It, will be obtained above in order to detect the chemical property for the nanoporous nickel nickel electrode material being prepared
Electrode for super capacitor material carries out cyclic voltammetry in 1mol/LKOH solution, and test uses CHI660e electrochemistry work
It stands, three-electrode system, nanoporous nickel nickel obtained above is working electrode, and gauze platinum electrode is auxiliary electrode, Ag/
AgCl electrode is reference electrode, and scanning speed 10mV/s, voltage range range is 0~0.5V.
Fig. 1 is the microscopic structure stereoscan photograph of nanoporous nickel nickel, prepared rodlike oxidation in this example
Nickel uniformly, dense growth in nanoporous nickel surface, 2 μm of the length of rodlike nickel oxide, the diameter of stick is about 0.3 μm.It simultaneously can
To find out, rodlike nickel oxide along the direction preferential growth perpendicular to collection liquid surface, region rodlike nickel oxide in nickel sheet
Coverage rate reaches 100% (area accounting).
Fig. 2 is the pattern photo of rodlike nickel oxide under high power, can be clearly observed rodlike 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 stick made from this example
The main component of shape structure organization is nickel and oxygen, and the percentage of nickel and oxygen shows the club shaped structure generated for oxidation close to 1:1
Nickel.Minimal amount of Zr element, Ti element and Al element exist in power spectrum result, show Zr, Ti, Al element on band surface layer de-
It is selectively dissolved substantially in alloy process.
Fig. 4 is the X ray diffracting spectrum of nanoporous nickel, to nanoporous nickel nickel obtained in the present embodiment
Phase composition carries out X-ray diffractogram spectrum analysis, shows that material made from this example is made of elemental nickel and nickel oxide, illustrates original
Ti element, Zr element, Al element in alloy strip are removed by selective corrosion, and success is prepared on nanoporous nickel
To rodlike nickel oxide.
Fig. 5 is nanoporous nickel nickel combination electrode material obtained measures in the present embodiment CV curve (by making
It is measured with CHI660e electrochemical workstation).With the area of curve enclosed region to characterize material specific capacitance value, it is computed to obtain and compares
Capacitance is 1504.8F/cm3, the 847.9F/cm that is obtained than first technology CN104269278A377.5% is improved, is shown very
Specific capacitance characteristic outstanding.
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
It is that pure Ni 8.140g, pure Ti stick 3.144g, pure Zr stick 7.703g, the pure Al piece 1.103g of 99.9wt.% is mixed to get mother
Then the raw metal mixed is placed in vacuum arc furnace ignition by alloy raw material 20g, the pure titanium for being 99.9wt.% by 20g purity
It is independently placed in vacuum arc furnace ignition and is not contacted with master alloy raw material, as oxygen scavenging material melting；Under protection of argon gas, melting is repeated
4 master alloys, 40 seconds or so every time, to ensure alloy structure uniformity；Room temperature is cooled to the furnace after the completion of melting, can be obtained
Ni42.5(Ti0.35Zr0.45Al0.20)57.5Alloy cast ingot (master alloy).
By the master alloy obtained after melting remove surface scale and be cut into it is suitably sized be placed in quartz ampoule, benefit
Band machine is got rid of with vacuum and prepares amorphous alloy ribbon, preparation condition are as follows: vacuum degree 9.0 × 10-4Pa blows casting pressure 0.1MPa, copper
Roller revolving speed is 35m/s.Master alloy is placed in quartz ampoule, molten state is heated under the protective atmosphere of argon gas blows cast closing at amorphous
Gold bar band prepares 47 μm thick, width 2cm alloy strip；
Second step, de- alloy prepare nanoporous nickel
5cm is taken from above-mentioned alloy strip, is placed in 0.5M hydrofluoric acid corrosive liquid at room temperature and is carried out de- alloy treatment
60min, then by sample with deionized water repeated flushing 3 times；
Third step, oxidation immersion-heat treatment prepare rodlike nickel oxide
Nanoporous nickel bar band obtained above is placed in KOH and H2O2Impregnate 6h in mixed liquor, the mixed liquor by
1.5mol/LKOH 40ml and 30wt.%H2O220ml composition；After immersion, takes out sample and rinsed 3 times with deionized water, set
Heat treatment 1h is carried out in the heat-treatment furnace that temperature is 250 DEG C, it is 1.0 × 10 that sample, which is put into vacuum degree, after heat treatment- 1It is saved in MPa vacuum oven.
Fig. 6 is nickel sheet/nickel oxide microscopic structure stereoscan photograph, it is seen that when reducing de- alloy time and oxidation immersion
Between after, the production quantity of rodlike nickel oxide is reduced, but still maintains continuous, uniform shape characteristic, 1 μ of nickel oxide stick length
M, the diameter of stick are 0.3 μm.Cyclic voltammetric survey is carried out to the nanoporous nickel nickel electrode material prepared in the present embodiment
Examination, condition and parameter with embodiment 1, be computed specific capacitance value be 1418.4F/cm3, obtained than first technology CN104269278A
847.9F/cm3Improve 67.3%.It decreases compared to embodiment 1, this shows that the content of nickel oxide is directly affected 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, it is equal to weigh mass fraction
Female conjunction is mixed to get for the pure Ni 7.647g of 99.9wt.%, pure Ti stick 3.275g, pure Zr stick 8.023g, pure Al piece 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 the pure titanium of 99.9wt.%
It is placed in vacuum arc furnace ignition and is not contacted with master alloy raw material, as oxygen scavenging material melting；Under protection of argon gas, melting 4 is repeated
Secondary master alloy, 40 seconds or so every time, to ensure alloy structure uniformity；Room temperature is cooled to the furnace after the completion of melting, can be obtained
Ni40(Ti0.35Zr0.45Al0.20)60Alloy cast ingot (master alloy).
By the master alloy obtained after melting remove surface scale and be cut into it is suitably sized be placed in quartz ampoule, benefit
Band machine is got rid of with vacuum and prepares amorphous alloy ribbon, preparation condition are as follows: vacuum degree 9.0 × 10-4Pa blows casting pressure 0.1MPa, copper
Roller revolving speed is 36m/s.Master alloy is placed in quartz ampoule, molten state is heated under the protective atmosphere of argon gas blows cast closing at amorphous
Gold bar band prepares 42 μm thick, width 2cm alloy strip；
Second step, de- alloy prepare nanoporous nickel
5cm is taken from above-mentioned alloy strip, is placed in progress removal alloying processing in 0.4M hydrofluoric acid corrosive liquid at room temperature
30min, then by sample with deionized water repeated flushing 3 times；
Third step, oxidation immersion-heat treatment prepare rodlike nickel oxide
Nanoporous nickel bar band obtained above is placed in KOH and H2O2Impregnate 4h in mixed liquor, the mixed liquor by
1mol/L KOH 40ml and 30wt.%H2O220ml composition；After immersion, takes out sample and rinsed 3 times with deionized water, is placed in
Heat treatment 1h is carried out in the heat-treatment furnace that temperature is 210 DEG C, it is 1.0 × 10 that sample, which is put into vacuum degree, after heat treatment-1MPa
Vacuum oven in save.
The microscopic structure stereoscan photograph of nanoporous nickel nickel obtained, rodlike nickel oxide in Fig. 7 the present embodiment
Production quantity significantly reduce, region inner area coverage rate is about 80%, nickel oxide stick in cluster-shaped aggregation growth, 1 μm of length, directly
About 0.2 μm of diameter.Cyclic voltammetry, test-strips are carried out to the nanoporous nickel nickel electrode material prepared in the present embodiment
Part and parameter with embodiment 1, be computed specific capacitance value be 1167.6F/cm3, obtained than first technology CN104269278A
847.9F/cm3Improve 37.8%.
Comparative example 1
Hydrofluoric acid solution concentration used in de- alloy is selected as 0.3M, and other conditions take off sample surfaces after alloy with embodiment 1
Uniform nano-porous structure is not formed, sample surfaces are generated without rodlike nickel oxide after simultaneous oxidation immersion-heat treatment.
Comparative example 2
After de- alloy, sample is in KOH and H2O22h is impregnated in mixed liquor, other conditions are the same as embodiment 1, the results showed that nanometer
The rodlike nickel oxide of the small size (length is less than 1 μm) for the scattered distribution that porous nickel surface only has quantity few, is prepared
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, as a result other conditions are shown with embodiment 1
Show: nanoporous nickel surface is generated without rodlike nickel oxide.
Comparative example 4
KOH solution and H are replaced with the NaOH solution of 2mol/L2O2Mixing, other conditions are with embodiment 1, the results show that receiving
Rice porous nickel surface does not generate rodlike nickel oxide.
Comparative example 5
It is the Ni-Ti-Zr-Al alloy of 35at.% that subject alloy, which selects nickel element content, and other conditions are the same as embodiment 2, hair
The alloy strip poor mechanical property being now prepared, brittleness are larger.After taking off alloy 60min in 0.5M HF, sample etches are broken
At small, it is unable to maintain that the mechanical integrity of initial cut.
The 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
A great deal of, equally distributed rodlike nickel oxide is obtained, thus nanoporous nickel/oxygen of electrochemical performance cannot be prepared
Change nickel electrode for super capacitor material.
Above embodiments and comparative example show the nanoporous nickel nickel electrode for super capacitor material in the present invention
The preparation method of material is arrived with labour income through a large number of experiments, by continuously attempting to, constantly gropes just to obtain optimal
Process conditions.The only parameter of each process procedure of strict control could successfully obtain the nanoporous of electrochemical performance
Nickel nickel electrode material.
Unaccomplished matter of the present invention is well-known technique.
Claims (3)
1. a kind of nanoporous nickel nickel electrode material for super capacitor, it is characterized in that the 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, two sides are nanoporous nickel layer；Rodlike nickel oxide is dispersed in nanoporous nickel surface, stick as active material
The hexagonal prism shape of rule is presented in shape nickel oxide, and stick length is 1 ~ 2 μm, and diameter is 0.1 ~ 0.3 μm；
The ni-based amorphous alloy ingredient is Ni40+x(Ti0.35Zr0.45Al0.20)60-x, x=0~5；Wherein, subscript number in alloy
Word is each element atomic percentage；
The nanoporous nickel nickel electrode material for super capacitor is made by following methods, comprising the following steps:
The first step prepares Ni-Ti-Zr-Al presoma AMORPHOUS ALLOY RIBBONS
According to the atomic percent of each element in subject alloy, pure Ni, pure Ti, pure Zr, pure Al totally 20 g are taken, by mixed conjunction
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 ingot is made；Band is got rid of in vacuum
The alloy cast ingot of acquisition is heated to molten condition in machine, is quickly blown out aluminium alloy using inert gas, makes the liquid of melting
Metal quickly solidifies on high-speed rotating copper roller, prepares 40 ~ 50 μm thick, wide 2 cm AMORPHOUS ALLOY RIBBONS, the conjunction
Golden ingredient are as follows: Ni40+x(Ti0.35Zr0.45Al0.20)60-x, x=0~5；Wherein, index number is each element atomic percent in alloy
Number；
The vacuum gets rid of band machine preparation condition are as follows: vacuum degree is 9.0 × 10-4 Pa；Pressure needed for blowing casting is 0.1MPa；Blow casting
Required copper roller revolving speed is 34-36 m/s；
Second step, de- alloy prepare 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；
The acid solution is hydrofluoric acid, and solution concentration is 0.4 ~ 0.6 M;
Third step, oxidation immersion-heat treatment prepare rodlike nickel oxide
Nanoporous nickel made from second step is placed in 4 ~ 8 h of immersion in mixed solution, after being rinsed after taking-up with deionized water, is set
0.5 ~ 1.5 h of heat treatment is carried out in heat-treatment furnace, temperature is set as 210 ~ 250 DEG C, and nanoporous nickel/oxygen is obtained after heat treatment
Change nickel electrode material for super capacitor；
The mixed solution is KOH solution and H2O2Solution mixes, and KOH concentration is 1 ~ 2 mol/L, H2O2Concentration is 30
Wt.%, mixed volume ratio are KOH solution: H2O2 Solution=2:1.
2. the preparation method of nanoporous nickel nickel electrode material for super capacitor as described in claim 1, it is characterized in that
The purity of described Ni, Ti, Zr, Al are 99.9 wt.%.
3. the preparation method of nanoporous nickel nickel electrode material for super capacitor as described in claim 1, it is characterized in that
The inert gas is the high-purity argon gas of purity 99.99%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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-
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Non-Patent Citations (3)
| Title |
|---|
| Facile fabrication of porous NiO films for lithium-ion batteries with high reversibility and rate capability;Qinmin Pan等;《J Solid State Electrochem》;20081202;第13卷;第1591-1597页 |
| 多孔氧化镍膜的制备及其赝电容性能;蔡荆等;《中国科技论文》;20150930;第10卷(第8期);第2106-2109页 |
| 纳米多孔镍/氧化镍的制备及其性能的研究;王丽娟;《中国优秀硕士学位论文全文数据库工程科技I辑》;20160715;第13-32页 |
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