CN106847528B - A kind of preparation method of novel nano oxide super capacitor electrode material - Google Patents
A kind of preparation method of novel nano oxide super capacitor electrode material Download PDFInfo
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- CN106847528B CN106847528B CN201710004292.XA CN201710004292A CN106847528B CN 106847528 B CN106847528 B CN 106847528B CN 201710004292 A CN201710004292 A CN 201710004292A CN 106847528 B CN106847528 B CN 106847528B
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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
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Abstract
The invention discloses a kind of preparation methods of novel nano oxide super capacitor electrode material, porous nano oxide and the aqueous solution of glucose or fructose are sufficiently mixed by this method, and solid product heated, after separation is the porous nano oxide containing hydroxyl；Contain the porous nano oxide of hydroxyl as electrode material for super capacitor using this, the electrode of super capacitor of the porous nano oxide preparation containing hydroxyl, when current density is 1A/g, specific capacitance value is 600~1000F/g, is remarkably improved super capacitor performance.
Description
Technical field
The present invention relates to a kind of electrode material for super capacitor, more particularly, refer to one kind in porous oxide nanometer
The super capacitance electrode material and preparation method thereof of particle surface introducing hydroxyl.
Background technique
In recent years, supercapacitor obtains extensive concern as a kind of novel energy-storing element.Compared with carbon material, transition
Metal oxide can provide bigger energy density and power density and become research hotspot.Wherein nickel oxide, four oxidations three
Cobalt etc. is considered as the electrode material for super capacitor of great potential due to high theoretical capacitance.However due to its conductivity
It is low, so that actual capacitance value is far below theoretical value.Therefore, the electric conductivity for improving electrode material becomes key urgently to be solved and asks
Topic.Currently, people mainly utilize the polyhydroxy such as glucose, fructose aldehyde or polyhydroxyketone to wrap on electrode material for super capacitor surface
Carbon-coating is covered, to improve the electric conductivity of electrode, improves its super capacitor performance, but still not over polyhydroxy such as glucose, fructose
Aldehyde or polyhydroxyketone improve the research report of super capacitor performance in electrode material for super capacitor surface introducing functional group.
Summary of the invention
An object of the present invention is to provide a kind of porous nano oxide containing hydroxyl, the porous nano oxide at
Be divided into containing hydroxyl porous nickel oxide (NiO) cladding nickel (Ni) nano particle or be the porous nickel cobalt oxide containing hydroxyl
Compound (NiO, CoO) coats the nano particle of nickel cobalt (Ni-Co) alloy or is the porous nickel cobalt oxide containing hydroxyl
(NiO,Co3O4) cladding nickel cobalt (Ni-Co) alloy nano particle.
The second object of the present invention is to provide one kind by glucose or fructose (polyhydroxy aldehyde or polyhydroxyketone) porous
NiO cladding Ni (or porous (NiO, CoO) cladding Ni-Co alloy or porous (NiO, Co3O4) cladding Ni-Co alloy) nano particle
Surface introduces the electrode material for super capacitor of hydroxyl, which has higher specific capacitance value, and the hydroxyl is as hydrophilic
Property functional group, the hydroxide ion in alkaline electrolyte can be made rapidly to penetrate into porous nano particle, improve ion expand
Rate is dissipated, to improve the electric conductivity of electrode material；Meanwhile the hydroxyl improves the electro-chemical activity of nano particle, so that through
The super capacitor performance of electrode material for super capacitor prepared by the present invention is improved.
The third object of the present invention is to provide a kind of method that hydroxyl is introduced in electrode material for super capacitor, this method
Porous NiO is coated into Ni (or porous (NiO, CoO) cladding Ni-Co alloy or porous (NiO, Co3O4) cladding Ni-Co alloy) receive
Rice grain and the aqueous solution of glucose or fructose (polyhydroxy aldehyde or polyhydroxyketone) are sufficiently mixed, and porous oxide nano particle is inhaled
Attached (chemisorption and physical absorption) by glucose or fructose (polyhydroxy aldehyde or polyhydroxyketone) aqueous solution because hemiacetal react
The free hydroxyl group of generation, to obtain the electrode material of the porous nano oxide containing hydroxyl.This method and process process letter
Single, raw material and process costs it is low, it is pollution-free, be suitable for large-scale production.
The method for preparing a kind of electrode of super capacitor containing hydroxyl of the invention includes preparation containing the more of hydroxyl
The step of hole nano-oxide and the step of preparing electrode of super capacitor；
The step of porous nano oxide prepared containing hydroxyl are as follows:
Step 1, hot plasma prepare alloy pig
Nickel (Ni) metal, aluminium (Al) metal or cobalt (Co) metal are smelted into Ni- by different atomic ratios in an inert atmosphere
Al bianry alloy ingot or Ni-Co-Al ternary alloy three-partalloy ingot, multiple melting make alloy pig distributed components.
The inert atmosphere is high-purity argon gas, and percent by volume purity is 99.999%.
The mass percent purity of nickel (Ni) metal is 99.9%.
The mass percent purity of cobalt (Co) metal is 99.9%.
The mass percent purity of aluminium (Al) metal is 99.9%.
Melting condition include: plasma operating current be 100A~500A, Plasma Center temperature be 4000 DEG C~
6000 DEG C, smelting time is 1~10min, and argon gas keeps 0.05~0.1MPa in fusion process.
Step 2, hydrogen plasma reaction prepare nano particle
Under the atmosphere of argon gas and hydrogen, by Ni-Al bianry alloy ingot made from step 1 or Ni-Co-Al ternary alloy three-partalloy
Ingot melts under the action of hot plasma, and Ni, Al or Co and hydrogen plasma is made to react, and passes through chemical vapor deposition
Prepare Ni-Al or Ni-Co-Al alloy nanoparticle.
Hydrogen plasma reaction condition includes: that the volume ratio of argon gas and hydrogen is 9:1~1:9, reacts furnace gas stagnation pressure
Power is 0.08~0.1MPa, and plasma current is 100~500A, and the reaction time is 5~200min.
Step 3 prepares porous nano particle
Ni-Al or Ni-Co-Al nano particle made from step 2 is subjected to removal alloying reaction under certain condition, so
Afterwards being washed products therefrom repeatedly with deionized water and ethyl alcohol to pH value is 7, and is passivated in air, and porous NiO is finally obtained
Coat the nano particle of Ni or (NiO, CoO) cladding Ni-Co alloy.
Removal alloying reaction condition includes: that removal alloying temperature is 20 DEG C~80 DEG C, and the concentration of sodium hydroxide solution is 10
~25wt%, processing time are 5~60min.
Step 4 prepares the porous nano particle containing hydroxyl
Porous nano particle made from step 3 is sufficiently mixed with certain density glucose or fructose aqueous solution, then
It pours into water heating kettle, handles certain time at a certain temperature, cooled to room temperature is finally collected solid-state with permanent magnet and produced
Object, and washed repeatedly through deionized water and ethyl alcohol, obtain the porous nano particle containing hydroxyl.
Treatment conditions include: that the concentration of glucose or fructose aqueous solution is 0.3~1.5g/L, and treatment temperature is 20 DEG C~
200 DEG C, processing the time be 3~for 24 hours.
Described the step of preparing electrode of super capacitor are as follows:
By the porous nano oxide made from step 4 containing hydroxyl with active carbon and polytetrafluoroethylene (PTFE) according to mass ratio
It is fully ground for 7:1:2 after being mixed into slurries, is applied in the nickel foam cleaned by 1cm × 1cm, then put it into drying
In case, drying for 24 hours, finally obtains the electrode of super capacitor that can carry out electro-chemical test at 60 DEG C.
Dosage: the porous nano oxide in above-mentioned electrode containing hydroxyl is 10mg.
In the present invention, the porous nano oxide successfully prepared and contain hydroxyl in surface is handled by glucose or fructose
Electrode material for super capacitor.The electrode of super capacitor of the porous nano oxide preparation containing hydroxyl, in electric current
When density is 1A/g, specific capacitance value is 600~1000F/g.
In the present invention, porous nickel cobalt oxide (NiO, Co in order to obtain3O4) cladding nickel cobalt (Ni-Co) alloy nanometer
Particle needs to be heat-treated the particle after removal alloying before step 4.
Heat treatment condition includes: that heat treatment temperature is 100 DEG C~500 DEG C, and heat treatment time is 1~3h.
Advantages of the present invention:
1. the technical process for preparing the porous nano oxide containing hydroxyl is simple and easy, environmentally protective, cost of material is low
It is honest and clean, and the content of hydroxyl can be adjusted by the concentration of regulation glucose or fructose aqueous solution, treatment temperature, processing time.
2. the electrode material for super capacitor through the porous nano oxide made from the method for the present invention containing hydroxyl, has
High conductivity and high electrochemical activity.
3. the electrode material for super capacitor through the porous nano oxide made from the method for the present invention containing hydroxyl, because containing
There is hydrophilic hydroxy functional group, the hydroxide ion in alkaline electrolyte is made to be easier to penetrate into porous nano particle, thus
The electric conductivity of electrode of super capacitor is improved, while hydroxy functional group improves the electrochemistry work of electrode material for super capacitor
Property, so that electrode of super capacitor has high specific capacitance value.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of the porous NiO cladding Ni nano particle containing hydroxyl.
Fig. 2 is the transmission electron microscope photo of the porous NiO cladding Ni nano particle containing hydroxyl.
Fig. 3 is the infrared microscopy map of the porous NiO cladding Ni nano particle containing hydroxyl.
Fig. 4 is the constant current charge-discharge curve of the porous NiO cladding Ni nano particle containing hydroxyl.
Fig. 5 is the constant current charge-discharge curve of porous (NiO, CoO) cladding Ni-Co alloy nanoparticle containing hydroxyl.
Specific embodiment
Below in conjunction with drawings and examples, the present invention is described in further detail.
In the present invention, the step of preparing the porous nano oxide containing hydroxyl are as follows:
Step 1, hot plasma prepare alloy pig
Nickel (Ni) metal, aluminium (Al) metal or cobalt (Co) metal are smelted into Ni- by different atomic ratios in an inert atmosphere
Al bianry alloy ingot or Ni-Co-Al ternary alloy three-partalloy ingot, multiple melting make alloy pig distributed components.
The inert atmosphere is high-purity argon gas, and percent by volume purity is 99.999%.
The mass percent purity of nickel (Ni) metal is 99.9%.
The mass percent purity of cobalt (Co) metal is 99.9%.
The mass percent purity of aluminium (Al) metal is 99.9%.
Melting condition include: plasma operating current be 100A~500A, Plasma Center temperature be 4000 DEG C~
6000 DEG C, smelting time is 1~10min, and argon gas keeps 0.05~0.1MPa in fusion process.
Step 2, hydrogen plasma reaction prepare nano particle
Under the atmosphere of argon gas and hydrogen, by Ni-Al bianry alloy ingot made from step 1 or Ni-Co-Al ternary alloy three-partalloy
Ingot melts under the action of hot plasma, and Ni, Al or Co and hydrogen plasma is made to react, and passes through chemical vapor deposition
Prepare Ni-Al or Ni-Co-Al alloy nanoparticle.
Hydrogen plasma melting condition are as follows: the volume ratio of argon gas and hydrogen is 9:1~1:9, total gas pressure in reacting furnace
For 0.08~0.1MPa, plasma current is 100~500A, and the reaction time is 5~200min.
Step 3 prepares porous nano particle
Ni-Al or Ni-Co-Al nano particle obtained is subjected to removal alloying reaction under certain condition, is then spent
It is 7 that ionized water and ethyl alcohol, which wash products therefrom repeatedly to pH value, and is passivated in air, and porous nano particle is finally obtained.
Removal alloying reaction condition includes: that removal alloying temperature is 20 DEG C~80 DEG C, and the concentration of sodium hydroxide solution is 10
~25wt%, removal alloying time are 5~60min.
Step 4 prepares the porous nano particle containing hydroxyl
Porous nano particle made from step 3 is sufficiently mixed with certain density glucose or fructose aqueous solution, then
It pours into water heating kettle, handles certain time at a certain temperature, cooled to room temperature is finally collected solid-state with permanent magnet and produced
Object, and washed repeatedly through deionized water and ethyl alcohol, obtain the porous nano particle containing hydroxyl.
Treatment conditions include: that the concentration of glucose or fructose aqueous solution is 0.3~1.5g/L, and treatment temperature is 20 DEG C~
200 DEG C, processing the time be 3~for 24 hours.
Described the step of preparing electrode are as follows:
By the porous nano oxide made from step 4 containing hydroxyl with active carbon and polytetrafluoroethylene (PTFE) according to mass ratio
It is fully ground for 7:1:2 after being mixed into slurries and is applied in the nickel foam cleaned by 1cm × 1cm, then put it into drying
In case, drying for 24 hours, finally obtains the electrode of super capacitor that can carry out electro-chemical test at 60 DEG C.
Dosage: the porous nano oxide in above-mentioned electrode containing hydroxyl is 10mg.
In the present invention, (NiO, Co in order to obtain3O4) cladding Ni-Co alloy nano particle, needed before step 4
Particle after removal alloying is heat-treated.
Heat treatment condition includes: that heat treatment temperature is 100 DEG C~500 DEG C, and heat treatment time is 1~3h.
Embodiment 1
Prepare the side of the electrode of super capacitor of porous nickel oxide (NiO) cladding nickel (Ni) nano particle containing hydroxyl
Method comprising have the step of preparing porous nickel oxide (NiO) cladding nickel (Ni) nano particle and prepare electrode of super capacitor
Step:
Described the step of preparing porous NiO cladding Ni nano particle are as follows:
Step 1, hot plasma prepare Ni-Al alloy pig
In the present invention, nickel (Ni) metal and aluminium (Al) metal are smelted into Ni-Al by atomic ratio 1:1 in an inert atmosphere
Alloy pig, makes Ni-Al alloy pig distributed components melting 3 times.
Melting condition includes: that plasma operating current is 220A, and plasma central temperature is 4700 DEG C, and smelting time is
5min, argon gas keeps 0.1MPa in fusion process.
The inert atmosphere is high-purity argon gas, and percent by volume purity is 99.999%.
The mass percent purity of nickel (Ni) metal is 99.9%.
The mass percent purity of aluminium (Al) metal is 99.9%.
Step 2, hydrogen plasma reaction preparation Ni-Al alloy nanoparticle
In the present invention, in the case where the volume ratio of argon gas and hydrogen is the reaction atmosphere of 1:1, by Ni-Al made from step 1
Alloy pig melts under hot plasma effect, and nickel, aluminium and hydrogen plasma is made to react, by chemical vapor deposition system
Standby Ni-Al alloy nanoparticle out；Average particle size particle size is 24nm.
Hydrogen plasma reaction condition include: in reacting furnace total gas pressure be 0.1MPa, plasma current 260A, instead
It is 90min between seasonable.
Step 3: removal alloying obtains porous NiO cladding Ni nano particle
Ni-Al alloy nanoparticle made from step 2 is subjected to removal alloying reaction in the NaOH solution of 20wt%,
Then washing product deionized water and ethyl alcohol to pH value repeatedly is 7, and is passivated in air, and porous NiO packet is finally obtained
Cover the nano particle of Ni；Removal alloying processing in the present invention is that the Al removal in Ni-Al alloying pellet is obtained porous
Looks.
Removal alloying reaction condition includes: that the sodium hydroxide of the 20wt% of addition 100mL in 0.2g alloy nanoparticle is molten
Liquid, removal alloying temperature are 80 DEG C, reaction time 10min.
Step 4: porous NiO of the preparation containing hydroxyl coats Ni nano particle
The cladding Ni nano particle of porous NiO made from step 3 is sufficiently mixed with glucose solution, is subsequently poured into water
Hot kettle, is put into drying box, and 3h is kept at 25 DEG C, and cooled to room temperature is finally collected solid product with permanent magnet, and passed through
Deionized water and ethyl alcohol wash repeatedly, obtain the porous NiO cladding Ni nano particle containing hydroxyl.
Dosage: it is in 1g/L glucose solution that the porous NiO cladding Ni nano particle of 0.1g, which is added to 50mL concentration,.
Permanent magnet is used in the present invention and collects magnetism NiO cladding Ni nano particle, makes to collect obtained porous NiO cladding
Ni nano particle purity is higher, and the method collection rate is high, simple, easy to operate.
Absorption of the porous nano particle to free hydroxyl group in glucose is applied in the present invention, and acquisition contains the porous of hydroxyl
NiO coats Ni nano particle；With electrode of super capacitor prepared by the nano particle, because containing hydrophilic hydroxy group, and make electrode
With high electro-chemical activity and high electric conductivity, so as to improve the super capacitor performance of electrode of super capacitor.With price
Donor of the cheap glucose as hydroxyl, at low cost, pollution-free, preparation process is simple and easy.
The step of preparing electrode of super capacitor are as follows:
By made from step 4 containing hydroxyl porous NiO cladding Ni nano particle and active carbon and polytetrafluoroethylene (PTFE) according to
Mass ratio is after 7:1:2 is fully ground and is mixed into slurries, to be applied in the nickel foam cleaned by 1cm × 1cm, then put
Enter in drying box, drying for 24 hours, finally obtains the electrode of super capacitor that can carry out electro-chemical test at 60 DEG C.
Dosage: the porous NiO cladding Ni nano particle in above-mentioned electrode containing hydroxyl is 10mg.
The porous of hydroxyl is contained to made from the step four in embodiment 1 using D/max-2200PC type X-ray diffractometer
NiO coats Ni nano particle and carries out material phase analysis, as shown in Figure 1, acquisition contains in the glucose solution of 25 DEG C of 1g/L
Having the porous NiO cladding Ni nanoparticles of hydroxyl mutually most of is W metal, exists simultaneously a certain amount of oxide NiO.
Hydroxyl is contained to made from the step four in embodiment 1 using JEOL-JSM-2100F type transmission electron microscope
Porous NiO cladding Ni nano particle carries out morphology analysis, as shown in Fig. 2, it can be observed that the porous NiO containing hydroxyl coats Ni
Nano particle porous shape characteristic spherical in shape, average particle size particle size 50nm.
The more of hydroxyl are contained to made from the step four in embodiment 1 using the micro ft-ir spectroscopy instrument of Spotlight200
Hole NiO coats Ni nano particle and carries out test analysis, as shown in Figure 3, it is known that the porous NiO containing hydroxyl coats Ni nano particle
In have the presence of a large amount of hydroxy functional group.Using the electrochemical workstation of CHI660E model to obtained super in embodiment 1
Electrode for capacitors carry out the test of super capacitor performance, as shown in Figure 4, the results showed that, the electrode current density be 1A/g when
Specific capacitance value reaches 929F/g.This is because being existed by the nano grain surface of the processed porous NiO cladding Ni of glucose big
Hydrophilic hydroxyl is measured, makes porous nano particle that there is higher electro-chemical activity, while alkaline electrolyte being made to be easier to permeate
Into in electrode of super capacitor, the electric conductivity of electrode is improved, to obtain high specific capacitance value.
Embodiment 2
Prepare the nano particle of porous nickel cobalt oxide (NiO, CoO) cladding nickel cobalt (Ni-Co) alloy containing hydroxyl
The method of electrode of super capacitor comprising prepare porous nickel cobalt oxide (NiO, CoO) cladding nickel cobalt (Ni-Co) alloy and receive
The step of rice grain and the step of preparing electrode of super capacitor:
Described the step of preparing porous (NiO, CoO) cladding Ni-Co alloy nanoparticle are as follows:
Step 1, hot plasma prepare Ni-Co-Al alloy pig
In the present invention, nickel (Ni) metal, cobalt (Co) metal and aluminium (Al) metal are pressed into atomic ratio 9 in an inert atmosphere:
38.5:52.5 is smelted into Ni-Co-Al alloy pig, makes Ni-Co-Al alloy pig distributed components melting 3 times；
Melting condition includes: that plasma operating current is 360A, and plasma central temperature is 5500 DEG C, and smelting time is
3min, argon gas keeps 0.08MPa in fusion process.
The inert atmosphere is high-purity argon gas, and percent by volume purity is 99.999%.
The mass percent purity of nickel (Ni) metal is 99.9%.
The mass percent purity of cobalt (Co) metal is 99.9%.
The mass percent purity of aluminium (Al) metal is 99.9%.
Step 2, hydrogen plasma reaction preparation Ni-Co-Al alloy nanoparticle
In the present invention, in the case where the volume ratio of argon gas and hydrogen is the reaction atmosphere of 1:2, by Ni-Co- made from step 1
Al alloy pig melts under hot plasma effect, and nickel, cobalt, aluminium and hydrogen plasma is made to react, and passes through chemical gaseous phase
Deposition prepares Ni-Co-Al alloy nanoparticle.
Hydrogen plasma reaction condition include: in reacting furnace total gas pressure be 0.1MPa, plasma current 250A, instead
It is 100min between seasonable.
Step 3: removal alloying obtains the nano particle of porous (NiO, CoO) cladding Ni-Co alloy
It is anti-that Ni-Co-Al alloy nanoparticle made from step 2 is carried out to removal alloying in the NaOH solution of 20wt%
It answers, then washing product deionized water and ethyl alcohol to pH value repeatedly is 7, and is passivated in air, is finally obtained porous
The nano particle of (NiO, CoO) cladding Ni-Co alloy.
Removal alloying reaction condition includes: that the sodium hydroxide of the 20wt% of addition 100mL in 0.2g alloy nanoparticle is molten
Liquid, removal alloying temperature are 80 DEG C, reaction time 10min.
Step 4: the nano particle of porous (NiO, CoO) cladding Ni-Co alloy of the preparation containing hydroxyl
(NiO, CoO) porous made from step 3 cladding Ni-Co alloy nanoparticle is sufficiently mixed with fructose aqueous solution,
It is subsequently poured into water heating kettle, is put into drying box, 3h is kept at 25 DEG C, cooled to room temperature is finally collected with permanent magnet solid
State product, and washed repeatedly through deionized water and ethyl alcohol, it obtains porous (NiO, CoO) cladding Ni-Co alloy containing hydroxyl and receives
Rice grain.
Dosage: it is 1g/L fruit that the nano particle of porous (NiO, CoO) cladding Ni-Co alloy of 0.1g, which is added to 50mL concentration,
In sugar aqueous solution.
Monosaccharide of the fructose as polyhydroxyketone generates free hydroxyl since hemiacetal reaction occurs in aqueous solution,
Porous (NiO, CoO) cladding Ni-Co alloy nanoparticle is because having high surface-active easily to adsorb hydroxyl simultaneously, so formed
The nano particle of porous (NiO, CoO) cladding Ni-Co alloy containing hydroxyl, coats Ni-Co alloy with this porous (NiO, CoO)
Nano particle made from electrode material for super capacitor be attached with hydrophilic hydroxy group because of surface, to improve the electrification of electrode
Activity and electric conductivity are learned, and then improves its super capacitor performance.
The step of preparing electrode of super capacitor are as follows:
By made from step 4 containing hydroxyl porous (NiO, CoO) cladding Ni-Co alloy nanoparticle and active carbon and
Polytetrafluoroethylene (PTFE) according to mass ratio be 7:1:2 be fully ground be mixed into slurries after the nickel foam cleaned is applied to by 1cm × 1cm
On, it then puts it into drying box, drying for 24 hours, finally obtains the supercapacitor that can carry out electro-chemical test at 60 DEG C
Electrode.
Dosage: porous (NiO, CoO) cladding Ni-Co alloy nanoparticle in above-mentioned electrode containing hydroxyl is 10mg.
Electricity is carried out to the electrode of supercapacitor obtained in embodiment 2 using the electrochemical workstation of CHI660E model
Chemical analysis, as shown in Figure 5, the results showed that, specific capacitance value of the electrode in the current density of 1A/g reaches 885F/g.The electricity
Pole is attached with a large amount of hydrophilies in the nano grain surface that porous (NiO, CoO) coats Ni-Co alloy by the processing of fructose
Hydroxy functional group, make (NiO, CoO) cladding Ni-Co alloy nanoparticle that there is higher electro-chemical activity, while making alkalinity
Electrolyte is easier to penetrate into electrode of super capacitor, improves the electric conductivity of electrode, to obtain high specific capacity.
Embodiment 3
Prepare the side of the electrode of super capacitor of porous nickel oxide (NiO) cladding nickel (Ni) nano particle containing hydroxyl
Method comprising have the step of preparing porous nickel oxide (NiO) cladding nickel (Ni) nano particle and prepare electrode of super capacitor
Step:
Described the step of preparing porous NiO cladding Ni nano particle are as follows:
Step 1, hot plasma prepare Ni-Al alloy pig
In the present invention, nickel (Ni) metal and aluminium (Al) metal are smelted into Ni-Al by atomic ratio 1:1 in an inert atmosphere
Alloy pig, makes Ni-Al alloy pig distributed components melting 3 times.
Melting condition includes: that plasma operating current is 100A, and plasma central temperature is 4000 DEG C, and smelting time is
10min, argon gas keeps 0.08MPa in fusion process.
The inert atmosphere is high-purity argon gas, and percent by volume purity is 99.999%.
The mass percent purity of nickel (Ni) metal is 99.9%.
The mass percent purity of aluminium (Al) metal is 99.9%.
Step 2, hydrogen plasma reaction preparation Ni-Al alloy nanoparticle
In the present invention, in the case where the volume ratio of argon gas and hydrogen is the reaction atmosphere of 1:8, by Ni-Al made from step 1
Alloy pig melts under hot plasma effect, and nickel, aluminium and hydrogen plasma is made to react, by chemical vapor deposition system
Standby Ni-Al alloy nanoparticle out.
Hydrogen plasma melting condition include: in reacting furnace total gas pressure be 0.08MPa, plasma current 100A,
Reaction time is 150min.
Step 3: removal alloying obtains porous NiO cladding Ni nano particle
Ni-Al alloy nanoparticle made from step 2 is subjected to removal alloying reaction in the NaOH solution of 15wt%,
Then washing product deionized water and ethyl alcohol to pH value repeatedly is 7, and is passivated in air, and porous NiO packet is finally obtained
Cover Ni nano particle.
Removal alloying reaction condition includes: that the sodium hydroxide of the 15wt% of addition 150mL in 0.2g alloy nanoparticle is molten
Liquid, removal alloying temperature are 50 DEG C, reaction time 60min.
Step 4: porous NiO of the preparation containing hydroxyl coats Ni nano particle
The cladding Ni nano particle of porous NiO made from step 3 is sufficiently mixed with glucose solution, is subsequently poured into water
Hot kettle, is put into drying box, and 6h is kept at 60 DEG C, and cooled to room temperature is finally collected solid product with permanent magnet, and passed through
Deionized water and ethyl alcohol wash repeatedly, obtain the porous NiO cladding Ni nano particle containing hydroxyl.
Dosage: it is in 1g/L glucose solution that the porous NiO cladding Ni nano particle of 0.1g, which is added to 50mL concentration,.
The step of preparing electrode of super capacitor are as follows:
By made from step 4 containing hydroxyl porous (NiO, CoO) cladding Ni-Co alloy nanoparticle and active carbon and
Polytetrafluoroethylene (PTFE) is that after 7:1:2 is fully ground and is mixed into slurries, the foam cleaned is applied to by 1cm × 1cm according to mass ratio
It on nickel, then puts it into drying box, drying for 24 hours, finally obtains the super capacitor that can carry out electro-chemical test at 60 DEG C
Device electrode.
Dosage: porous (NiO, CoO) cladding Ni-Co alloy nanoparticle in above-mentioned electrode containing hydroxyl is 10mg.
Electrification is carried out to electrode of super capacitor obtained in embodiment 3 using the electrochemical workstation of CHI660E model
Credit analysis, as a result specific capacitance value of the electrode when current density is 1A/g reaches 766F/g.
Embodiment 4
Prepare porous nickel cobalt oxide (NiO, Co containing hydroxyl3O4) cladding nickel cobalt (Ni-Co) alloy nano particle
The method of electrode of super capacitor comprising prepare porous nickel cobalt oxide (NiO, Co3O4) cladding nickel cobalt (Ni-Co) alloy
The step of nano particle and the step of preparing electrode of super capacitor:
It is described to prepare porous (NiO, Co3O4) cladding Ni-Co alloy nanoparticle the step of are as follows:
Step 1, hot plasma prepare Ni-Co-Al alloy pig
In the present invention, nickel (Ni) metal, cobalt (Co) metal and aluminium (Al) metal are pressed into atomic ratio 25 in an inert atmosphere:
22.5:52.5 is smelted into Ni-Co-Al alloy pig, makes Ni-Co-Al alloy pig distributed components melting 3 times.
Melting condition includes: plasma operating current 180A, and plasma central temperature is 4300 DEG C, and smelting time is
6min, argon gas keeps 0.09MPa in fusion process.
The inert atmosphere is high-purity argon gas, and percent by volume purity is 99.999%.
The mass percent purity of nickel (Ni) metal is 99.9%.
The mass percent purity of cobalt (Co) metal is 99.9%.
The mass percent purity of aluminium (Al) metal is 99.9%.
Step 2, hydrogen plasma reaction preparation Ni-Co-Al alloy nanoparticle
In the present invention, in the case where the volume ratio of argon gas and hydrogen is the reaction atmosphere of 1:1, by Ni-Co- made from step 1
Al alloy pig melts under hot plasma effect, and nickel, cobalt, aluminium and hydrogen plasma is made to react, and passes through chemical gaseous phase
Deposition prepares Ni-Co-Al alloy nanoparticle.
Hydrogen plasma melting condition include: in reacting furnace total gas pressure be 0.1MPa, plasma current 180A, instead
It is 160min between seasonable.
Step 3: removal alloying obtains porous (NiO, Co3O4) cladding Ni-Co alloy nano particle
It is anti-that Ni-Co-Al alloy nanoparticle made from step 2 is carried out to removal alloying in the NaOH solution of 20wt%
It answers, later washing product deionized water and ethyl alcohol to pH value repeatedly is 7, and is passivated in air, finally hot at 150 DEG C
2h is handled, porous (NiO, Co are obtained3O4) cladding Ni-Co alloy nanoparticle.
Removal alloying reaction condition includes: that the sodium hydroxide of the 25wt% of addition 100mL in 0.2g alloy nanoparticle is molten
Liquid, removal alloying temperature are 60 DEG C, reaction time 5min.
Step 4: porous (NiO, Co of the preparation containing hydroxyl3O4) cladding Ni-Co alloy nano particle
.By porous (NiO, Co made from step 33O4) cladding Ni-Co alloy nanoparticle and fructose aqueous solution it is sufficiently mixed
It closes, is subsequently poured into water heating kettle, is put into drying box, kept at 180 DEG C for 24 hours, cooled to room temperature is finally received with permanent magnet
Collect solid product, and washed repeatedly through deionized water and ethyl alcohol, obtains porous (NiO, the Co containing hydroxyl3O4) cladding Ni-Co conjunction
Gold nano grain.
Dosage: porous (NiO, the Co of 0.1g3O4) cladding Ni-Co alloy nanoparticle be added to 50mL concentration be 0.3g/L
In fructose aqueous solution.
The step of preparing electrode of super capacitor are as follows:
By porous (NiO, the Co made from step 4 containing hydroxyl3O4) cladding Ni-Co alloy nanoparticle and active carbon and
Polytetrafluoroethylene (PTFE) is that after 7:1:2 is fully ground and is mixed into slurries, the foam cleaned is applied to by 1cm × 1cm according to mass ratio
It on nickel, then puts it into drying box, drying for 24 hours, finally obtains the super capacitor that can carry out electro-chemical test at 60 DEG C
Device electrode.
Dosage: porous (NiO, Co in above-mentioned electrode containing hydroxyl3O4) cladding Ni-Co alloy nanoparticle be 10mg.
Electrification is carried out to electrode of super capacitor obtained in embodiment 4 using the electrochemical workstation of CHI660E model
Credit analysis, the results showed that the specific capacitance value of the electrode reaches 841F/g.
Embodiment 5
Prepare porous nickel cobalt oxide (NiO, Co containing hydroxyl3O4) cladding nickel cobalt (Ni-Co) alloy nano particle
The method of electrode of super capacitor comprising prepare porous nickel cobalt oxide (NiO, Co3O4) cladding nickel cobalt (Ni-Co) alloy
The step of nano particle and the step of preparing electrode of super capacitor:
It is described to prepare porous (NiO, Co3O4) cladding Ni-Co alloy nanoparticle the step of are as follows:
Step 1, hot plasma prepare Ni-Co-Al alloy pig
In the present invention, nickel (Ni) metal, cobalt (Co) metal and aluminium (Al) metal are pressed into atomic ratio in an inert atmosphere
15.5:32:52.5 is smelted into Ni-Co-Al alloy pig, makes Ni-Co-Al alloy pig distributed components melting 3 times.
Melting condition includes: that plasma operating current is 400A, and plasma central temperature is 5800 DEG C, and smelting time is
3min, argon gas keeps 0.09MPa in fusion process.
The inert atmosphere is high-purity argon gas, and percent by volume purity is 99.999%.
The mass percent purity of nickel (Ni) metal is 99.9%.
The mass percent purity of cobalt (Co) metal is 99.9%.
The mass percent purity of aluminium (Al) metal is 99.9%.
Step 2, hydrogen plasma reaction preparation Ni-Co-Al alloy nanoparticle
In the present invention, in the case where the volume ratio of argon gas and hydrogen is the reaction atmosphere of 3:5, by Ni-Co- made from step 1
Al alloy pig melts under hot plasma effect, and nickel, cobalt, aluminium and hydrogen plasma is made to react, and passes through chemical gaseous phase
Deposition prepares Ni-Co-Al alloy nanoparticle.
Hydrogen plasma melting condition include: in reacting furnace total gas pressure be 0.1MPa, plasma current 300A, instead
It is 60min between seasonable.
Step 3: removal alloying obtains porous (NiO, Co3O4) cladding Ni-Co alloy nano particle
It is anti-that Ni-Co-Al alloy nanoparticle made from step 2 is carried out to removal alloying in the NaOH solution of 20wt%
It answers, later washing product deionized water and ethyl alcohol to pH value repeatedly is 7, and is passivated in air, then hot at 500 DEG C
3h is handled, porous (NiO, Co are obtained3O4) cladding Ni-Co alloy nanoparticle.
Removal alloying reaction condition includes: that the sodium hydroxide of the 20wt% of addition 100mL in 0.2g alloy nanoparticle is molten
Liquid, removal alloying temperature are 30 DEG C, reaction time 10min.
Step 4: porous (NiO, Co of the preparation containing hydroxyl3O4) cladding Ni-Co alloy nano particle
By porous (NiO, Co made from step 33O4) cladding Ni-Co alloy nanoparticle and fructose aqueous solution it is sufficiently mixed
It closes, is subsequently poured into water heating kettle, is put into drying box, 8h is kept at 25 DEG C, cooled to room temperature is finally collected with permanent magnet
Solid product, and washed repeatedly through deionized water and ethyl alcohol, obtain porous (NiO, the Co containing hydroxyl3O4) cladding Ni-Co alloy
Nano particle.
Dosage: porous (NiO, the Co of 0.2g3O4) cladding Ni-Co alloy nanoparticle be added to 50mL concentration be 1.2g/L
In fructose aqueous solution.
The step of preparing electrode of super capacitor are as follows:
By porous (NiO, the Co made from step 4 containing hydroxyl3O4) cladding Ni-Co alloy nanoparticle and active carbon and
Polytetrafluoroethylene (PTFE) is that after 7:1:2 is fully ground and is mixed into slurries, the foam cleaned is applied to by 1cm × 1cm according to mass ratio
It on nickel, then puts it into drying box, drying for 24 hours, finally obtains the super capacitor that can carry out electro-chemical test at 60 DEG C
Device electrode.
Dosage: porous (NiO, Co in above-mentioned electrode containing hydroxyl3O4) cladding Ni-Co alloy nanoparticle be 10mg.
Electrification is carried out to electrode of super capacitor obtained in embodiment 5 using the electrochemical workstation of CHI660E model
Credit analysis, the results showed that the specific capacitance value of the electrode reaches 667F/g.
Claims (7)
1. a kind of preparation method of novel nano oxide super capacitor electrode material, it is characterised in that there is the following steps:
Porous nano oxide and the aqueous solution of certain density glucose or fructose are sufficiently mixed, water heating kettle is subsequently poured into
In, handle certain time at a certain temperature, cooled to room temperature finally collects solid product with permanent magnet, and gone from
Sub- water and ethyl alcohol wash repeatedly, obtain the porous nano oxide containing hydroxyl；
The porous nano oxide components are the nano particle that porous nickel cobalt oxide coats nickel cobalt (alloy)；The porous nickel cobalt oxide
The chemical formula of compound is NiO, CoO or NiO, Co3O4；
Treatment conditions include: that the concentration of glucose or fructose aqueous solution is 0.3~1.5g/L, and treatment temperature is 20 DEG C~200 DEG C,
Handle the time be 3~for 24 hours；
The nano grain surface of porous NiO obtained, CoO cladding Ni-Co alloy is attached with hydroxy functional group；
Porous NiO, Co obtained3O4The nano grain surface of cladding Ni-Co alloy is attached with hydroxy functional group.
2. a kind of preparation method of novel nano oxide super capacitor electrode material according to claim 1, special
Sign is: the electrode material is to coat the nano particle of Ni-Co alloy through the processed porous NiO of fructose, CoO.
3. a kind of preparation method of novel nano oxide super capacitor electrode material according to claim 1, special
Sign is: the electrode material is through the processed porous NiO of glucose, Co3O4Coat the nano particle of Ni-Co alloy.
4. a kind of preparation method of novel nano oxide super capacitor electrode material according to claim 1, special
Sign is: the electrode material is through the processed porous NiO of fructose, Co3O4Coat the nano particle of Ni-Co alloy.
5. a kind of preparation method of novel nano oxide super capacitor electrode material according to claim 1, special
Sign is: the porous nano particle of porous nickel cobalt oxide cladding nickel cobalt (alloy) is prepared with the following steps:
Step 1, hot plasma prepare alloy pig
Ni metal, Al metal and Co metal are smelted into Ni-Co-Al ternary alloy three-partalloy ingot by different atomic ratios in an inert atmosphere,
Multiple melting makes alloy pig distributed components；
The inert atmosphere is high-purity argon gas, and percent by volume purity is 99.999%；
The mass percent purity of the Ni metal is 99.9%；
The mass percent purity of the Co metal is 99.9%；
The mass percent purity of the Al metal is 99.9%；
Melting condition includes: that plasma operating current is 100A~500A, and Plasma Center temperature is 4000 DEG C~6000 DEG C,
Smelting time is 1~10min, and argon gas keeps 0.05~0.1MPa in fusion process；
Step 2, hydrogen plasma reaction prepare nano particle
Under the atmosphere of argon gas and hydrogen, by Ni-Co-Al ternary alloy three-partalloy ingot made from step 1 under the action of hot plasma
Fusing, and Ni, Al or Co and hydrogen plasma is made to react, Ni-Co-Al alloy nano is prepared by chemical vapor deposition
Particle；
Hydrogen plasma reaction condition includes: that the volume ratio of argon gas and hydrogen is 9:1~1:9, and total gas pressure is in reacting furnace
0.08~0.1MPa, plasma current are 100~500A, and the reaction time is 5~200min；
Step 3 prepares porous nano particle
Ni-Co-Al nano particle made from step 2 is subjected to removal alloying reaction under certain condition, then uses deionized water
Washing products therefrom to pH value repeatedly with ethyl alcohol is 7, and is passivated in air, and NiO is finally obtained, and CoO coats Ni-Co alloy
Porous nano particle；
Removal alloying reaction condition includes: that temperature is 20 DEG C~80 DEG C, and the concentration of sodium hydroxide solution is 10~25wt%, goes to close
The aurification time is 5~60min.
6. a kind of preparation method of novel nano oxide super capacitor electrode material according to claim 1, special
Sign is: the porous nano particle of porous nickel cobalt oxide cladding nickel cobalt (alloy) is prepared with the following steps:
Step 1, hot plasma prepare alloy pig
Ni metal, Al metal and Co metal are smelted into Ni-Co-Al ternary alloy three-partalloy ingot by different atomic ratios in an inert atmosphere,
Multiple melting makes alloy pig distributed components；
The inert atmosphere is high-purity argon gas, and percent by volume purity is 99.999%；
The mass percent purity of the Ni metal is 99.9%；
The mass percent purity of the Co metal is 99.9%；
The mass percent purity of the Al metal is 99.9%；
Melting condition includes: that plasma operating current is 100A~500A, and Plasma Center temperature is 4000 DEG C~6000 DEG C,
Smelting time is 1~10min, and argon gas keeps 0.05~0.1MPa in fusion process；
Step 2, hydrogen plasma reaction prepare nano particle
Under the atmosphere of argon gas and hydrogen, by Ni-Co-Al ternary alloy three-partalloy ingot made from step 1 under the action of hot plasma
Fusing, and Ni, Al or Co and hydrogen plasma is made to react, Ni-Co-Al alloy nano is prepared by chemical vapor deposition
Particle；
Hydrogen plasma reaction condition includes: that the volume ratio of argon gas and hydrogen is 9:1~1:9, and total gas pressure is in reacting furnace
0.08~0.1MPa, plasma current are 100~500A, and the reaction time is 5~200min；
Step 3 prepares porous nano particle
Ni-Co-Al nano particle made from step 2 is subjected to removal alloying reaction under certain condition, then uses deionized water
Washing products therefrom to pH value repeatedly with ethyl alcohol is 7, and is passivated in air, finally hot in 100 DEG C~500 DEG C of air
1~3h is handled, NiO, Co are obtained3O4Coat the porous nano particle of Ni-Co alloy；
Removal alloying reaction condition includes: that temperature is 20 DEG C~80 DEG C, and the concentration of sodium hydroxide solution is 10~25wt%, goes to close
The aurification time is 5~60min.
7. a kind of preparation method of novel nano oxide super capacitor electrode material according to claim 1, special
Sign is: the specific capacitance value of the electrode material reaches 600~1000F/g under the current density of 1A/g.
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