CN107275100A - A kind of ultracapacitor and preparation method thereof - Google Patents
A kind of ultracapacitor and preparation method thereof Download PDFInfo
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- CN107275100A CN107275100A CN201710650745.6A CN201710650745A CN107275100A CN 107275100 A CN107275100 A CN 107275100A CN 201710650745 A CN201710650745 A CN 201710650745A CN 107275100 A CN107275100 A CN 107275100A
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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
- H01G11/30—Electrodes 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to a kind of ultracapacitor and preparation method thereof, the sour Ni cluster of three-dimensional structure micron order cobalt is included in the positive active material of the ultracapacitor of the present invention, and three-dimensional porous activated carbon is included in negative electrode active material, wherein, the sour Ni cluster of the cobalt is the cluster that fold extension shape and surface have nanoneedle.The present invention passes through the sour Ni cluster of cobalt of specific morphology and three-dimensional porous activated carbon mating reaction, collaboration improves the chemical property of ultracapacitor, obtained ultracapacitor has higher electrochemical capacitor performance, with outstanding energy-storage property, very high energy density, power density and excellent cyclical stability.
Description
Technical field
The present invention relates to ultracapacitor positive and negative electrode material, and in particular to three-dimensional knot is included in a kind of positive active material
Structure micron order cobalt acid Ni cluster, and ultracapacitor comprising three-dimensional porous activated carbon and preparation method thereof in negative electrode active material
Porous carbon is prepared using template and prepares the sour nickel of cobalt using hydrothermal co-precipitation method.
Background technology
With the arrival of world energy sources crisis, environmentally friendly and sustainable development energy storage device and energy storage material are sought
Material, which turns into, becomes more and more important.Wherein ultracapacitor generally has excellent high-power charge-discharge performance, and power density is high,
Memory-less effect, fast charging and discharging has extended cycle life, the features such as ultracapacitor also has memory-less effect in addition, Yi Zhongjie
Novel energy-storing element between conventional capacitor and chemical cell, has the high specific power of traditional capacitor concurrently and chemical cell is high
Specific energy the characteristics of, so slowly start widely to study for people, and in telecommunications, communications and transportation, military affairs
It is used widely Deng field.
The good and bad capacitive property for directly determining device of electrode material, therefore, it is super that the exploitation of active electrode material, which becomes,
The emphasis of research and the application of level capacitor.
Metal oxide hydroxide mainly carries out energy storage by occurring redox reaction, due to metal oxidation
Produced pseudo-capacitance will be significantly larger than the electric double layer capacitance produced by carbon-based material to thing hydroxide in the reaction, wherein your gold
Belong to oxide (such as RuO2) there is very excellent electrochemical capacitance, but expensive price and hypertoxicity restrict its work significantly
For the application and commercialization of electrochemical capacitor electrode material, researcher attempts to prepare cobalt oxide (Co by distinct methods3O4)、
Nickel oxide (NiO), tin oxide (SnO2) and manganese oxide (MnOx) etc. base metal oxide, maximize retention property under the conditions of, make
For the substitute of metal oxide containing precious metals.The ternary material of particularly most emerging nickel cobalt oxygen shows good electrochemistry
Energy.
Especially wherein the cobalt of ternary, nickel oxide are easily prepared, and pattern change is easily controlled and shows different differences
Chemical property, research shows cobalt prepared at present, nickel oxide NiCo2O4Group easily occurs in traditional preparation process
It is poly- so that the oxide material specific surface area reduction of preparation.Other NiCo2O4The conductance of itself is relatively low so that high current density
The decay of lower specific capacitance and specific capacity is very fast, and high rate performance is poor.It is to improve it in supercapacitor applications to change its pattern
A research direction, such as A of CN 104701036 report a kind of based on classification flower-shape Ni Co2O4Electrode for super capacitor
Material, described electrode material for super capacitor is that the classification being directly grown on conductive substrates nickel screen by hydro-thermal method is flower-shaped
NiCo2O4, provided NiCo is provided2O4Preparation method obtained by flower-like structure be to be formed by nanometer sheet self assembly.
At present it has been reported that the pattern such as nano-wire array, nanometer sheet, sea urchin shape, though the electrode material of these specific morphologies
The specific capacity of capacitor is so improved to a certain extent, but is difficult to have excellent specific capacity and good cycle performance concurrently,
Thus, studying the electrode material of specific morphology and further applying it further to improve chemical property of capacitor has weight
The meaning wanted.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of ultracapacitor, this hair
The sour Ni cluster of the bright cobalt by specific morphology and three-dimensional porous activated carbon mating reaction, collaboration improve the electrification of ultracapacitor
Performance is learned, obtained ultracapacitor has higher electrochemical capacitor performance, very high with outstanding energy-storage property
Energy density, power density and excellent cyclical stability.
To achieve these goals, the present invention is adopted the technical scheme that：
Included in a first aspect, the present invention is provided in a kind of ultracapacitor, the positive active material of the ultracapacitor
Three-dimensional structure micron order cobalt acid Ni cluster, and three-dimensional porous activated carbon is included in negative electrode active material；
Wherein, the sour Ni cluster of the three-dimensional structure micron order cobalt is the cluster that fold extension shape and surface have nanoneedle.
In the present invention, the sour Ni cluster of pure three-dimensional structure micron order cobalt can be used as positive active material,
It can also be used cooperatively with other kinds of positive active material collectively as positive active material.Preferably use pure
The sour Ni cluster of three-dimensional structure micron order cobalt as positive active material so that ultracapacitor has more excellent performance.
In the present invention, pure three-dimensional porous activated carbon can be used as negative electrode active material, can also be with other species
Negative electrode active material use cooperatively collectively as negative electrode active material.Pure three-dimensional porous activated carbon is preferably used as negative pole
Active material, so that ultracapacitor has more excellent performance.
As the optimal technical scheme of ultracapacitor of the present invention, the positive active material of the ultracapacitor is
Three-dimensional structure micron order cobalt acid Ni cluster, and negative electrode active material is three-dimensional porous activated carbon, in such a case, it is possible to make to surpass
Level capacitor has more excellent chemical property.
The ultracapacitor of the present invention is preferably Asymmetric Supercapacitor.
Preferably, the three-dimensional dimension of the sour Ni cluster of the cobalt is at 1-2 μm, such as 1 μm, 1.2 μm, 1.3 μm, 1.5 μm, 1.6 μ
M, 1.7 μm, 1.8 μm or 2 μm etc..
Preferably, the specific surface area of the three-dimensional porous activated carbon is in 500-1100m2g-1, such as 500m2g-1、600m2g-1、700m2g-1、800m2g-1、900m2g-1、1000m2g-1Or 1100m2g-1Deng preferably 1100m2g-1。
Preferably, the aperture of the three-dimensional porous activated carbon is in 300-600nm, such as 300nm, 400nm, 450nm,
500nm, 550nm or 600nm etc., preferably 600nm.
Preferably, in the ultracapacitor, the matter of three-dimensional structure micron order cobalt acid Ni cluster and three-dimensional porous activated carbon
Ratio is measured in 0.5-1, such as 0.5,0.6,0.65,0.7,0.8,0.85,0.9 or 1.
Preferably, the gross mass using the sour Ni cluster of three-dimensional structure micron order cobalt, binding agent and carbon black is counted as 100wt%, and three
The weight/mass percentage composition for tieing up the sour Ni cluster of structure micron order cobalt is 80-85wt%, such as 80wt%, 82wt%, 83wt%,
84wt% or 85wt% etc.；The weight/mass percentage composition of binding agent be 10-5wt%, such as 10wt%, 9wt%, 8wt%, 7wt%,
6.5wt%, 6wt% or 5wt% etc.；The weight/mass percentage composition of carbon black be 10-5wt%, such as 10wt%, 8wt%, 7wt%,
6wt%, 5.5wt% or 5wt% etc..
Preferably, the gross mass using three-dimensional porous activated carbon, binding agent and carbon black is counted as 100wt%, three-dimensional porous activity
The weight/mass percentage composition of charcoal is 80-85wt%, such as 80wt%, 82wt%, 83wt% or 85wt%；The quality hundred of binding agent
It is 10-5wt%, 10wt%, 8wt%, 7wt%, 6wt% or 5wt% etc. to divide content；The weight/mass percentage composition of carbon black is 10-
5wt%, such as 10wt%, 8wt%, 7.5wt%, 7wt%, 6wt% or 5wt%.
Second aspect, the present invention provides the preparation method of ultracapacitor as described in relation to the first aspect, and methods described includes
Following steps：
(1) the sour Ni cluster of three-dimensional structure micron order cobalt is prepared：
By nickel source, cobalt source and urea according to 1:2:The mol ratio of (3-6) adds water scattered, obtains mixed solution；
In the liner that mixed solution is poured into water heating kettle, it is then placed in homogeneous reactor, in 120 DEG C of hydro-thermal reaction 0.5-
1.5h, then by hydrothermal product in 300-400 DEG C of calcining, obtain the sour Ni cluster of three-dimensional structure micron order cobalt；
(2) three-dimensional porous activated carbon is prepared：
Citric acid and NaCl are dissolved in deionized water, freeze-drying removes moisture, then carried out under protective atmosphere
Calcining, obtains three-dimensional porous activated carbon；
(3) ultracapacitor is prepared：
Use the positive active material of the sour Ni cluster of the three-dimensional structure micron order cobalt obtained comprising step (1), binding agent with
And carbon black prepares positive pole；
Prepared using the negative electrode active material, binding agent and carbon black of the three-dimensional porous activated carbon obtained comprising step (2) negative
Pole；
Ultracapacitor is prepared into using positive pole, negative pole, barrier film and electrolyte.
In step (1) of the present invention, the mol ratio of nickel source, cobalt source and urea is 1:2:(3-6), such as 1:2:3、1:2:3.5、
1:2:3.8、1:2:4、1:2:4.5 or 1:2:6 etc..Amount of the amount of the material of such as nickel source in 0.1-0.5mmol, the material of cobalt source
0.2-1mmol, the material of urea amount between 0.6-3mmol, and meet above-mentioned mol ratio relation.
In step (1) of the present invention, the time of hydro-thermal reaction is 0.5-1.5h, such as 0.5h, 0.8h, 1h, 1.2h or 1.5h
Deng.
In step (1) of the present invention, the temperature of calcining is 300-400 DEG C, such as 300 DEG C, 325 DEG C, 350 DEG C, 360 DEG C, 370
DEG C, 380 DEG C or 400 DEG C etc., preferably 300-350 DEG C.
As the optimal technical scheme of the method for the invention, in step (1), the nickel source is selected from NiSO4·6H2O、Ni
(NO3)2·6H2O or NiCl2·6H2In O any one or at least two combination.
Preferably, in step (1), the cobalt source is selected from CoSO4·7H2O、Co(NO3)2·6H2O or CoCl2·6H2In O
Any one or at least two combination.
Preferably, it is described to be separated into step (1)：Stir and ultrasonic disperse, the time of the stirring is preferably 30min.
Preferably, in step (1), it is additionally included in after the completion of disperseing, the step of continuing to stir 1h.
Preferably, in step (1), in the mixed solution, Ni molar concentration is 0.00588mol/L.
Preferably, in step (1), in the mixed solution, Co molar concentration is 0.0118mol/L.
Preferably, in step (1), in the mixed solution, the molar concentration of urea is 0.0353mol/L.
Preferably, in step (1), the liner of the water heating kettle is polytetrafluoroethyllining lining.
Preferably, in step (1), in addition to hydrothermal product be washed to the step of neutrality.
Preferably, in step (1), the heating rate of the calcining is 3-5 DEG C/min, such as 3 DEG C/min, 3.5 DEG C/min,
4 DEG C/min, 4.5 DEG C/min or 5 DEG C/min etc..
Preferably, in step (1), the soaking time of the calcining is 2-3h, for example, 2h, 2.2h, 2.3h, 2.6h,
2.8h or 3h etc..
In the method for the present invention, step (2) is using citric acid as carbon source, and NaCl is masterplate, deionized water is dissolved in, then true
It is freeze-dried under empty condition, moisture is thoroughly removed, then the high-temperature calcination under the conditions of protective gas, citric acid is carbonized,
So as to obtain three-dimensional porous activated carbon.
In step (2) of the present invention, citric acid, NaCl are dissolved in deionized water to NaCl and are completely dissolved.
As the optimal technical scheme of the method for the invention, in step (2), the mass ratio of the NaCl and citric acid are
(20-60):1, such as 20:1、30:1、40:1 or 60:1 etc., preferably 60:1.
Preferably, the step of freeze-drying is：The mixed solution of citric acid and sodium chloride is put into surface plate and uniformly spread
Keep flat in refrigerator and thoroughly freeze, be then placed in vacuum drying chamber and get rid of moisture using freeze-drying.
Preferably, in step (2), the protective atmosphere is nitrogen atmosphere.
Preferably, in step (2), the temperature of the calcining is 600-750 DEG C, such as 600 DEG C, 650 DEG C, 680 DEG C, 700
DEG C, 725 DEG C or 750 DEG C etc., preferably 750 DEG C.
Preferably, in step (2), time of the calcining is 1-3h, such as 1h, 1.2h, 1.5h, 1.7h, 2h, 2.5h or
3h etc., preferably 2h.
Preferably, in step (2), in addition to calcined product is washed, suction filtration and dries to remove the step of salting liquid
Suddenly.
As the optimal technical scheme of the method for the invention, in step (3), the three-dimensional structure micron order cobalt acid in positive pole
The mass ratio of Ni cluster and the three-dimensional porous activated carbon in negative pole is 0.5-1, such as 0.5,0.6,0.7,0.8 or 1.In this matter
In the range of amount ratio, the sour Ni cluster of three-dimensional structure micron order cobalt and the collaboration of three-dimensional porous activated carbon can be made to play a role, improve super
The chemical property of level capacitor.
Preferably, in step (3), using the gross mass of the sour Ni cluster of three-dimensional structure micron order cobalt, binding agent and carbon black as
100wt% is counted, and the weight/mass percentage composition of three-dimensional structure micron order cobalt acid Ni cluster is 80-85wt%, the quality percentage of binding agent
Content is 10-5wt%, and the weight/mass percentage composition of carbon black is 10-5wt%.
Preferably, in step (3), counted using the gross mass of three-dimensional porous activated carbon, binding agent and carbon black as 100wt%, three
The weight/mass percentage composition for tieing up porous activated carbon is 80-85wt%, and the weight/mass percentage composition of binding agent is 10-5wt%, the matter of carbon black
Amount percentage composition is 10-5wt%.
The method that step (3) of the present invention prepares ultracapacitor, can be method commonly used in the art, people in the art
Member can refer to prior art and be prepared, and the species of species and electrolyte to barrier film is not construed as limiting, and those skilled in the art can
Selected as needed, for example, can be polypropylene diaphragm, 3M KOH electrolyte.
Compared with the prior art, the present invention has the advantages that：
(1) present invention utilizes hydrothermal co-precipitation method, the mol ratio of control nickel source, cobalt source and urea, hydrothermal temperature, hydro-thermal
Time, and the parameter such as calcining heat, form the micron scale clusters of unique morphology, specifically fold extension shape and surface has
The cluster of nanoneedle, it is a kind of similar flower-shaped sour nickel of porous cobalt of three-dimensional, in the same size, is evenly distributed.
(2) by the use of the unique micron scale clusters of pattern of the present invention as positive electrode active materials, and conformability using three-dimensional
Porous activated carbon is as negative electrode active material, and above-mentioned specific micron scale clusters and three-dimensional porous activated carbon can cooperate with improvement super
The electric conductivity and chemical property of capacitor especially Asymmetric Supercapacitor.
(3) in ultracapacitor of the invention, it is preferred to use the sour Ni cluster of pure three-dimensional structure micron order cobalt is used as positive pole
Active material (is added without other kinds of active material), using pure three-dimensional porous activated carbon as negative electrode active material (no
Add other kinds of active material), the chemical property of ultracapacitor is not only improved, also realizes technique and more holds
Easily, pollution is decreased.
(4) preparation technology of the invention is simple, and obtained ultracapacitor has very high electrochemical capacitor performance, tool
There are outstanding energy-storage property, very high energy density, power density and excellent cyclical stability.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, without having to pay creative labor, may be used also
To obtain other accompanying drawings according to these accompanying drawings.
Fig. 1 a and Fig. 1 b are SEM figure of the three-dimensional porous activated carbon for preparing of embodiment 1 under different multiplying；
Fig. 1 c are the three-dimensional structure micron order NiCo that embodiment 1 is prepared2O4SEM figure；
Fig. 2 is three-dimensional structure micron order NiCo prepared by embodiment 12O4The X-ray diffraction pair of cluster and standard card
Than figure, wherein (i) represents standard card JCPDS No.20-0781, (ii) represents the three-dimensional structure micron order of the preparation of embodiment 1
NiCo2O4Cluster；
Fig. 3 is AC/NiCo prepared by embodiment 12O4Asymmetric Supercapacitor is in 1-100mVs-1Sweep the circulation volt under speed
Antu；
Fig. 4 is AC/NiCo prepared by embodiment 12O4Asymmetric Supercapacitor is in 1Ag-1；2Ag-1；3Ag-1；5Ag-1Electricity
Constant current charge-discharge diagram under current density；
Fig. 5 is AC/NiCo prepared by embodiment 12O4Asymmetric Supercapacitor is in 2Ag-1Circulation under current density is steady
Qualitative figure.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
A part of embodiment of the present invention, rather than whole embodiments.
Based on the embodiment in the present invention, those of ordinary skill in the art are obtained under the premise of creative work is not paid
The every other embodiment obtained, belongs to the scope of protection of the invention.
1) three-dimensional porous activated carbon is prepared：
The preparation early stage of three-dimensional porous activated carbon utilizes vacuum drying means, first goes citric acid and NaCl with a certain amount of
Ionized water is well mixed, and is then placed in be put into refrigerator in surface plate and is freezed, and then will be frozen real material and is put into freezing and do
In dry machine, moisture therein is thoroughly removed.Calcined using the tube furnace high temperature that can lead to protective gas, make citric acid charcoal
Change, filter out salting liquid using Suction filtration device, be finally putting into drying baker and be dried to obtain three-dimensional porous activated carbon.
2) three-dimensional structure micron order NiCo is prepared2O4Cluster：
By nickel source, cobalt source and urea according to 1:2:The mol ratio of (3-6) adds deionized water uniform using ultrasonic mixing.Use water
Thermal response kettle and homogeneous reactor are washed into the presoma of 120 DEG C of hydro-thermal reaction 0.5-1.5h synthesis precipitations with centrifuge
Property, it is put into drying baker and dries.Then with being calcined in atmosphere to presoma at 300-400 DEG C of low temperature in Muffle furnace.Finally
To the sour nickel of cobalt of black powder, it is possible to increase the specific capacity of sodium-ion battery is effectively improved the circulation of ultracapacitor.
3) prepared using above-mentioned three-dimensional porous activated carbon and the sour Ni cluster of three-dimensional structure micron order cobalt as active material
Asymmetric Supercapacitor.
4) electrical property detection is carried out to Asymmetric Supercapacitor：
In chi660d electrochemical workstations, positive pole is carried out and negative in 3M KOH solutions using three-electrode system first
The electro-chemical test of pole material.
When surveying positive electrode, the three-dimensional structure micron order NiCo in nickel foam is coated in2O4Cluster is used as working electrode, Pt
Piece and saturated calomel electrode are respectively as auxiliary electrode and reference electrode.
When surveying negative material, the three-dimensional porous activated carbon (being named as AC) being coated in nickel foam makees electrode, auxiliary electrode
With reference electrode ibid.
Below by specific embodiment, the present invention is further illustrated：
Embodiment 1
(1) preparation of three-dimensional porous activated carbon
It is template with NaCl, citric acid is carbon source, addition deionized water, which is stirred to sodium chloride, is completely dissolved (NaCl and lemon
The mass ratio of acid is 60:1), then uniform pave is put into refrigerator and thoroughly freezed in surface plate, is then placed in vacuum drying chamber
Moisture is got rid of using freeze-drying, is then placed in tube furnace and is passed through nitrogen protection progress high-temperature calcination, the temperature of high-temperature calcination
Spend for 750 DEG C, the soaking time of high-temperature calcination is 2h, is subsequently cooled to room temperature, prepares three-dimensional porous activated carbon, it has
600nm or so hole, specific surface area is in 1100m2g-1。
(2) three-dimensional structure micron order NiCo2O4Preparation
0.1mmol NiSO4·6H2O、0.2mmol CoSO4·7H2O and 0.6mmol urea, which adds water, to be stirred 30 minutes, is surpassed
Sound is stirred for a hour, is then placed in the water heating kettle of polytetrafluoroethyllining lining untill disperseing completely, is then placed in
In phase reaction device, 120 DEG C of heating-up temperature, hydro-thermal reaction (coprecipitation reaction i.e. under HTHP) 45min is cooled to after room temperature
The precipitation of liner is carried out to be washed to neutrality.
The sample of above-mentioned washing is dried, powder-like is put into Muffle furnace and calcined.Calcining heat is forged at 300 DEG C
Soaking time 3h is burnt, the sour Ni cluster of black powder, i.e. three-dimensional structure micron order cobalt is finally given.
It is prepared by positive pole：Active matter quality (NiCo2O4):Binding agent (5%PTFE):Acetylene black=8:1:1, by the material weighed up
Pour into Yan Portland and then add appropriate deionized water and stir, add binding agent and continue to stir to well mixed, coating
It is glossy into micro- thick, then it is coated in advance with the good 1.5cm of low-kappa number2Nickel foam on, coated area 1cm2, in advance
Reserve 0.5cm2For being sandwiched in electrode holder, coating is uniform, and non-foam nickel exposes, and is then dried in 60 DEG C of thermostatic drying chamber
It is dry, finally suppress flakiness.
It is prepared by negative pole：Active matter quality (three-dimensional porous carbon):Binding agent (5%PTFE):Acetylene black=8:1:1, it will weigh up
Material pour into Yan Portland and then add appropriate deionized water and stir, add binding agent and continue to stir to well mixed,
Coating is glossy into micro- thick, is then coated in advance with the good 1.5cm of low-kappa number2Nickel foam on, coated area
1cm2, reserve 0.5cm2For being sandwiched in electrode holder, coating is uniform, and non-foam nickel exposes, then in 60 DEG C of freeze-day with constant temperature
Dried in case, finally suppress flakiness.
Finally the positive and negative electrode of preparation is clamped respectively with electrode holder, electrolyte is done with 3M KOH, prepares AC/
NiCo2O4Asymmetric Supercapacitor, then carries out two electrode tests.
In the Asymmetric Supercapacitor of the present embodiment, three-dimensional structure micron order cobalt acid Ni cluster and three-dimensional porous activated carbon
Mass ratio calculated according to equation below：
Wherein R is mass ratio, C+And C-The respectively specific capacity of both positive and negative polarity, F/g and potential region (V), with the ratio under 1A/g
Capacity is defined, C+=625F/g, C-=218F/g.
The R values for calculating the present embodiment are 0.66.
Test result shows that the capacitor performance of the present embodiment is good.
Fig. 1 a and Fig. 1 b are SEM figure of the obtained three-dimensional porous activated carbon of the present embodiment under different multiplying, can be with by figure
Find out, even aperture distribution, and hole magnitude range is also consistent, illustrates that NaCl serves the effect of template well.
Fig. 1 c are the three-dimensional structure micron order NiCo that the present embodiment is obtained2O4SEM figure, as seen from the figure, obtained production
Thing is a kind of sour Ni cluster structure of three-dimensional structure micron order cobalt of dispersed surface with a small amount of nano whiskers structure.
Fig. 2 is the three-dimensional structure micron order NiCo of the present embodiment2O4The X-ray diffraction comparison diagram of cluster and standard card, its
In (i) represent standard card JCPDS No.20-0781, (ii) represents the three-dimensional structure micron order NiCo of the preparation of embodiment 12O4Group
Cluster, as seen from the figure, obtained product three-dimensional structure micron order NiCo2O4Cluster and NiCo2O4The peak value of standard card is relative
Should.
Fig. 3 is the AC/NiCo that the present embodiment is obtained2O4Asymmetric Supercapacitor is in 1-100mVs-1Sweep the circulation under speed
Voltammogram, as seen from the figure, electrochemical window broaden, substantially without redox peaks, and with the increase for sweeping speed, remain to
Original pattern is kept to illustrate that cyclicity is preferable.
Fig. 4 is the AC/NiCo that the present embodiment is obtained2O4Asymmetric Supercapacitor is in 1Ag-1；2Ag-1；3Ag-1；5Ag-1Electricity
Constant current charge-discharge diagram under current density, as seen from the figure, 5Ag is increased to current density-1When and 1Ag-1Compared to than electricity
Appearance is maintained at 90.6%, illustrates that cycle performance is good.
Fig. 5 is AC/NiCo prepared by embodiment 12O4Asymmetric Supercapacitor is in 2Ag-1Circulation under current density is steady
Qualitative figure, as seen from the figure, specific capacitance is unstable at the beginning, decay, may and test environment, it is relevant with electrode material, but
With the increase in cycle, almost do not decay, illustrate under larger current density, symmetrical device can keep good stable
Property.
Embodiment 2
(1) prepared by three-dimensional porous activated carbon
It is template with NaCl, citric acid is carbon source, addition deionized water, which is stirred to sodium chloride, to be completely dissolved, (NaCl and lemon
The mass ratio of lemon acid is 60:1), then uniform pave is put into refrigerator and thoroughly freezed in surface plate, is then placed in vacuum drying chamber
Moisture is got rid of in middle utilization freeze-drying, is then placed in tube furnace and is passed through nitrogen protection progress high-temperature calcination, high-temperature calcination
Temperature is 750 DEG C, and the soaking time of high-temperature calcination is 2h, is subsequently cooled to room temperature, prepares three-dimensional porous activated carbon, it has
600nm or so hole, specific surface area is in 1100m2g-1。
(2) three-dimensional structure micron order NiCo2O4Preparation
0.1mmol NiSO4·6H2O、0.2mmol CoSO4·7H2O and 0.6mmol urea, which adds water, to be stirred 30 minutes, is entered
Row ultrasonic disperse more than 30 minutes, untill disperseing completely, is stirred for a hour, is then placed in polytetrafluoroethyllining lining
In water heating kettle, it is then placed in homogeneous reactor, 120 DEG C of heating-up temperature, (co-precipitation i.e. under HTHP is anti-for hydro-thermal reaction
Should) 1h, it is cooled to after room temperature and carries out the precipitation of liner to be washed to neutrality.
The sample of above-mentioned washing is dried, powder-like is put into Muffle furnace and calcined.Calcining heat is forged at 300 DEG C
Soaking time 3h is burnt, the sour Ni cluster of black powder, i.e. three-dimensional structure micron order cobalt is finally given.
It is prepared by positive pole：Active matter quality (NiCo2O4):Binding agent (5%PTFE):Acetylene black=8.5:0.5:1, it will weigh up
Material pour into Yan Portland and then add appropriate deionized water and stir, add binding agent and continue to stir to well mixed,
Coating is glossy into micro- thick, is then coated in advance with the good 1.5cm of low-kappa number2Nickel foam on, coated area
1cm2, reserve 0.5cm2For being sandwiched in electrode holder, coating is uniform, and non-foam nickel exposes, then in 60 DEG C of freeze-day with constant temperature
Dried in case, finally suppress flakiness.
It is prepared by negative pole：Active matter quality (three-dimensional porous carbon):Binding agent (5%PTFE):Acetylene black=8:1:1, it will weigh up
Material pour into Yan Portland and then add appropriate deionized water and stir, add binding agent and continue to stir to well mixed,
Coating is glossy into micro- thick, is then coated in advance with the good 1.5cm of low-kappa number2Nickel foam on, coated area
1cm2, reserve 0.5cm2For being sandwiched in electrode holder, coating is uniform, and non-foam nickel exposes, then in 60 DEG C of freeze-day with constant temperature
Dried in case, finally suppress flakiness.
Finally the positive and negative electrode of preparation is clamped respectively with electrode holder, electrolyte is done with 3M KOH, is prepared asymmetric
Ultracapacitor, then carries out two electrode tests.
Using the method sour Ni cluster of calculating three-dimensional structure micron order cobalt and three-dimensional porous activated carbon same as Example 1
Mass ratio, result of calculation is R=0.66.
Test result shows that the capacitor performance of the present embodiment is good.
Embodiment 3
(1) prepared by three-dimensional porous activated carbon
It is template with NaCl, citric acid is carbon source, addition deionized water, which is stirred to sodium chloride, is completely dissolved (NaCl and lemon
The mass ratio of acid is 60:1), then uniform pave is put into refrigerator and thoroughly freezed in surface plate, is then placed in vacuum drying chamber
Moisture is got rid of using freeze-drying, is then placed in tube furnace and is passed through nitrogen protection progress high-temperature calcination, the temperature of high-temperature calcination
Spend for 750 DEG C, the soaking time of high-temperature calcination is 2h, is subsequently cooled to room temperature, prepares three-dimensional porous activated carbon, it has
600nm or so hole, specific surface area is in 1100m2g-1。
(2) three-dimensional structure micron order NiCo2O4Preparation
0.4mmolNiSO4·6H2O、0.8mmolCoSO4.·7H2O and 1.2mmol urea, which adds water, to be stirred 30 minutes, is carried out
Ultrasonic disperse more than 30 minutes, untill disperseing completely, is stirred for a hour, is then placed in the water of polytetrafluoroethyllining lining
In hot kettle, it is then placed in homogeneous reactor, 120 DEG C of heating-up temperature, hydro-thermal reaction (coprecipitation reaction i.e. under HTHP)
0.5h, is cooled to after room temperature and carries out the precipitation of liner to be washed to neutrality.
The sample of above-mentioned washing is dried, powder-like is put into Muffle furnace and calcined.Calcining heat is forged at 300 DEG C
Soaking time 3h is burnt, the sour Ni cluster of black powder, i.e. three-dimensional structure micron order cobalt is finally given.
It is prepared by positive pole：Active matter quality (NiCo2O4):Binding agent (5%PTFE):Acetylene black=8:1:1, by the material weighed up
Pour into Yan Portland and then add appropriate deionized water and stir, add binding agent and continue to stir to well mixed, coating
It is glossy into micro- thick, then it is coated in advance with the good 1.5cm of low-kappa number2Nickel foam on, coated area 1cm2, in advance
Reserve 0.5cm2For being sandwiched in electrode holder, coating is uniform, and non-foam nickel exposes, and is then dried in 60 DEG C of thermostatic drying chamber
It is dry, finally suppress flakiness.
It is prepared by negative pole：Active matter quality (three-dimensional porous carbon):Binding agent (5%PTFE):Acetylene black=8:1:1, it will weigh up
Material pour into Yan Portland and then add appropriate deionized water and stir, add binding agent and continue to stir to well mixed,
Coating is glossy into micro- thick, is then coated in advance with the good 1.5cm of low-kappa number2Nickel foam on, coated area
1cm2, reserve 0.5cm2For being sandwiched in electrode holder, coating is uniform, and non-foam nickel exposes, then in 60 DEG C of freeze-day with constant temperature
Dried in case, finally suppress flakiness.
Finally the positive and negative electrode of preparation is clamped respectively with electrode holder, electrolyte is done with 3M KOH, is prepared asymmetric
Ultracapacitor, then carries out two electrode tests.
Using the method sour Ni cluster of calculating three-dimensional structure micron order cobalt and three-dimensional porous activated carbon same as Example 1
Mass ratio, result of calculation is R=0.8.
Test result shows that the capacitor performance of the present embodiment is good.
Embodiment 4
(1) prepared by three-dimensional porous activated carbon
It is template with NaCl, citric acid is carbon source, addition deionized water, which is stirred to sodium chloride, is completely dissolved (NaCl and lemon
The mass ratio of acid is 60:1), then uniform pave is put into refrigerator and thoroughly freezed in surface plate, is then placed in vacuum drying chamber
Moisture is got rid of using freeze-drying, is then placed in tube furnace and is passed through nitrogen protection progress high-temperature calcination, the temperature of high-temperature calcination
Spend for 750 DEG C, the soaking time of high-temperature calcination is 2h, is subsequently cooled to room temperature, prepares three-dimensional porous activated carbon, and it has height
600nm or so hole is prepared in temperature calcining, and specific surface area is in 1100m2g-1。
(2) three-dimensional structure micron order NiCo2O4Preparation
0.4mmolNiSO4·6H2O、0.8mmolCoSO4·7H2O and 1.2mmol urea, which adds water, to be stirred 30 minutes, is carried out
Ultrasonic disperse more than 30 minutes, untill disperseing completely, is stirred for a hour, is then placed in the water of polytetrafluoroethyllining lining
In hot kettle, it is then placed in homogeneous reactor, 120 DEG C of heating-up temperature, hydro-thermal reaction (coprecipitation reaction i.e. under HTHP)
1h, is cooled to after room temperature and carries out the precipitation of liner to be washed to neutrality.
The sample of above-mentioned washing is dried, powder-like is put into Muffle furnace and calcined.Calcining heat is forged at 300 DEG C
Soaking time 3h is burnt, the sour Ni cluster of black powder, i.e. three-dimensional structure micron order cobalt is finally given.
It is prepared by positive pole：Active matter quality (NiCo2O4):Binding agent (5%PTFE):Acetylene black=75:10:15, by what is weighed up
Material pours into Yan Portland and then adds appropriate deionized water and stirs, and adds binding agent and continues to stir to well mixed, applies
Expect into it is micro- thick, it is glossy, be then coated in advance with the good 1.5cm of low-kappa number2Nickel foam on, coated area 1cm2,
Reserve 0.5cm2For being sandwiched in electrode holder, coating is uniform, and non-foam nickel exposes, then in 60 DEG C of thermostatic drying chamber
Drying, finally suppresses flakiness.
It is prepared by negative pole：Active matter quality (three-dimensional porous carbon):Binding agent (5%PTFE):Acetylene black=8:1:1, it will weigh up
Material pour into Yan Portland and then add appropriate deionized water and stir, add binding agent and continue to stir to well mixed,
Coating is glossy into micro- thick, is then coated in advance with the good 1.5cm of low-kappa number2Nickel foam on, coated area
1cm2, reserve 0.5cm2For being sandwiched in electrode holder, coating is uniform, and non-foam nickel exposes, then in 60 DEG C of freeze-day with constant temperature
Dried in case, finally suppress flakiness.
Finally the positive and negative electrode of preparation is clamped respectively with electrode holder, electrolyte is done with 3M KOH, is prepared asymmetric
Ultracapacitor, then carries out two electrode tests.
Using the method sour Ni cluster of calculating three-dimensional structure micron order cobalt and three-dimensional porous activated carbon same as Example 1
Mass ratio, result of calculation is R=0.8.
Test result shows that the capacitor performance of the present embodiment is good.
Embodiment 5
(1) prepared by three-dimensional porous activated carbon
It is template with NaCl, citric acid is carbon source, addition deionized water, which is stirred to sodium chloride, is completely dissolved (NaCl and lemon
The mass ratio of acid is 60:1), then uniform pave is put into refrigerator and thoroughly freezed in surface plate, is then placed in vacuum drying chamber
Moisture is got rid of using freeze-drying, is then placed in tube furnace and is passed through nitrogen protection progress high-temperature calcination, the temperature of high-temperature calcination
Spend for 750 DEG C, the soaking time of high-temperature calcination is 2h, is subsequently cooled to room temperature, prepares three-dimensional porous activated carbon, it has
600nm or so hole, specific surface area is in 1100m2g-1。
(2) three-dimensional structure micron order NiCo2O4Preparation
0.3mmol Ni(SO4)2.·6H2O、0.6mmol Co(SO4)2.·7H2O and 1.8mmol urea, which adds water, stirs 30 points
Clock, then carries out ultrasonic disperse more than 30 minutes, untill disperseing completely, is stirred for a hour, is then placed in polytetrafluoro
In the water heating kettle of ethene liner, it is then placed in homogeneous reactor, 120 DEG C of heating-up temperature, hydro-thermal reaction is (i.e. under HTHP
Coprecipitation reaction) 1h, it is cooled to after room temperature and carries out the precipitation of liner to be washed to neutrality.
The sample of above-mentioned washing is dried, powder-like is put into Muffle furnace and calcined.Calcining heat is forged at 350 DEG C
Soaking time 3h is burnt, the sour Ni cluster of black powder, i.e. three-dimensional structure micron order cobalt is finally given.
It is prepared by positive pole：Active matter quality (NiCo2O4):Binding agent (5%PTFE):Acetylene black=8:1:1, by the material weighed up
Pour into Yan Portland and then add appropriate deionized water and stir, add binding agent and continue to stir to well mixed, coating
It is glossy into micro- thick, then it is coated in advance with the good 1.5cm of low-kappa number2Nickel foam on, coated area 1cm2, in advance
Reserve 0.5cm2For being sandwiched in electrode holder, coating is uniform, and non-foam nickel exposes, and is then dried in 60 DEG C of thermostatic drying chamber
It is dry, finally suppress flakiness.
It is prepared by negative pole：Active matter quality (three-dimensional porous carbon):Binding agent (5%PTFE):Acetylene black=8:1:1, it will weigh up
Material pour into Yan Portland and then add appropriate deionized water and stir, add binding agent and continue to stir to well mixed,
Coating is glossy into micro- thick, is then coated in advance with the good 1.5cm of low-kappa number2Nickel foam on, coated area
1cm2, reserve 0.5cm2For being sandwiched in electrode holder, coating is uniform, and non-foam nickel exposes, then in 60 DEG C of freeze-day with constant temperature
Dried in case, finally suppress flakiness.
Finally the positive and negative electrode of preparation is clamped respectively with electrode holder, electrolyte is done with 3M KOH, is prepared asymmetric
Ultracapacitor, then carries out two electrode tests.
Using the method sour Ni cluster of calculating three-dimensional structure micron order cobalt and three-dimensional porous activated carbon same as Example 1
Mass ratio, result of calculation is R=0.7.
Test result shows that the capacitor performance of the present embodiment is good.
Comparative example 1
Except by three-dimensional structure micron order NiCo2O4Replace with outside NiO, other preparation methods and condition are same as Example 1.
The specific capacitance of the ultracapacitor of this comparative example uses NiCo less than embodiment 12O4Do the three-dimensional porous carbon of positive pole and do negative pole
Asymmetric capacitor specific capacitance.
Comparative example 2
In addition to three-dimensional porous activated carbon, which is replaced with, does activated carbon after maize straw carbonization, other preparation methods and condition with
Embodiment 1 is identical.
The specific capacitance of the ultracapacitor of this comparative example uses NiCo less than embodiment 12O4Do the three-dimensional porous carbon of positive pole and do negative pole
Asymmetric capacitor specific capacitance.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. a kind of ultracapacitor, it is characterised in that micro- comprising three-dimensional structure in the positive active material of the ultracapacitor
Meter level cobalt acid Ni cluster, and three-dimensional porous activated carbon is included in negative electrode active material；
Wherein, the sour Ni cluster of the three-dimensional structure micron order cobalt is the cluster that fold extension shape and surface have nanoneedle.
2. ultracapacitor according to claim 1, it is characterised in that the ultracapacitor is asymmetric super capacitor
Device；
Preferably, the three-dimensional dimension of the sour Ni cluster of the cobalt is at 1-2 μm；
Preferably, the specific surface area of the three-dimensional porous activated carbon is in 500-1100m2g-1, preferably 1100m2g-1；
Preferably, the aperture of the three-dimensional porous activated carbon is in 300-600nm, preferably 600nm.
3. ultracapacitor according to claim 1 or 2, it is characterised in that in the ultracapacitor, three-dimensional structure is micro-
The mass ratio of meter level cobalt acid Ni cluster and three-dimensional porous activated carbon is in 0.5-1.
4. the ultracapacitor according to claim any one of 1-3, it is characterised in that with the sour nickel of three-dimensional structure micron order cobalt
The gross mass of cluster, binding agent and carbon black is counted for 100wt%, and the weight/mass percentage composition of three-dimensional structure micron order cobalt acid Ni cluster is
80-85wt%, the weight/mass percentage composition of binding agent is 10-5wt%, and the weight/mass percentage composition of carbon black is 10-5wt%；
Preferably, the gross mass using three-dimensional porous activated carbon, binding agent and carbon black is counted as 100wt%, three-dimensional porous activated carbon
Weight/mass percentage composition is 80-85wt%, and the weight/mass percentage composition of binding agent is 10-5wt%, and the weight/mass percentage composition of carbon black is
10-5wt%.
5. the preparation method of the ultracapacitor according to claim any one of 1-4, it is characterised in that methods described includes
Following steps：
(1) the sour Ni cluster of three-dimensional structure micron order cobalt is prepared：
By nickel source, cobalt source and urea according to 1:2:The mol ratio of (3-6) adds water scattered, obtains mixed solution；
In the liner that mixed solution is poured into water heating kettle, it is then placed in homogeneous reactor, in 120 DEG C of hydro-thermal reaction 0.5-
1.5h, then by hydrothermal product in 300-400 DEG C of calcining, obtain the sour Ni cluster of three-dimensional structure micron order cobalt；
(2) three-dimensional porous activated carbon is prepared：
Citric acid, NaCl are dissolved in deionized water, freeze-drying removes moisture, is then calcined under protective atmosphere,
Obtain three-dimensional porous activated carbon；
(3) ultracapacitor is prepared：
Using positive active material, binding agent and the charcoal of the sour Ni cluster of the three-dimensional structure micron order cobalt obtained comprising step (1)
It is black to prepare positive pole；
Negative pole is prepared using negative electrode active material, binding agent and the carbon black of the three-dimensional porous activated carbon obtained comprising step (2)；
Ultracapacitor is prepared into using positive pole, negative pole, barrier film and electrolyte.
6. method according to claim 5, it is characterised in that in step (1), the nickel source is selected from NiSO4·6H2O、Ni
(NO3)2·6H2O or NiCl2·6H2In O any one or at least two combination；
Preferably, in step (1), the cobalt source is selected from CoSO4·7H2O、Co(NO3)2·6H2O or CoCl2·6H2It is any in O
It is a kind of or at least two combination；
Preferably, it is described to be separated into step (1)：Stir and ultrasonic disperse, the time of the stirring is preferably 30min；
Preferably, in step (1), it is additionally included in after the completion of disperseing, the step of continuing to stir 1h；
Preferably, in step (1), in the mixed solution, Ni molar concentration is 0.00588mol/L；
Preferably, in step (1), in the mixed solution, Co molar concentration is 0.0118mol/L；
Preferably, in step (1), in the mixed solution, the molar concentration of urea is 0.0353mol/L；
Preferably, in step (1), the liner of the water heating kettle is polytetrafluoroethyllining lining；
Preferably, in step (1), in addition to hydrothermal product be washed to the step of neutrality.
Preferably, in step (1), the heating rate of the calcining is 3-5 DEG C/min；
Preferably, in step (1), the temperature of the calcining is 300-350 DEG C；
Preferably, in step (1), the soaking time of the calcining is 2-3h.
7. the method according to claim 5 or 6, it is characterised in that in step (2), the quality of the NaCl and citric acid
Than for (20-60):1, preferably 60:1；
Preferably, in step (2), the protective atmosphere is nitrogen atmosphere；
Preferably, in step (2), the temperature of the calcining is 600-750 DEG C, preferably 750 DEG C；
Preferably, in step (2), the time of the calcining is 1-3h, preferably 2h.
8. the method according to claim any one of 5-7, it is characterised in that in step (3), the three-dimensional structure in positive pole is micro-
The mass ratio of meter level cobalt acid Ni cluster and the three-dimensional porous activated carbon in negative pole is 0.5-1.
9. the method according to claim any one of 5-8, it is characterised in that in step (3), with three-dimensional structure micron order cobalt
The gross mass of sour Ni cluster, binding agent and carbon black is counted for 100wt%, and the quality percentage of three-dimensional structure micron order cobalt acid Ni cluster contains
Measure as 80-85wt%, the weight/mass percentage composition of binding agent is 10-5wt%, and the weight/mass percentage composition of carbon black is 10-5wt%；
Preferably, in step (3), counted using the gross mass of three-dimensional porous activated carbon, binding agent and carbon black as 100wt%, it is three-dimensional many
The weight/mass percentage composition of mesoporous activated carbon is 80-85wt%, and the weight/mass percentage composition of binding agent is 10-5wt%, the quality hundred of carbon black
It is 10-5wt% to divide content.
10. the method according to claim any one of 5-9, it is characterised in that the described method comprises the following steps：
(1) the sour Ni cluster of three-dimensional structure micron order cobalt is prepared：
By nickel source, cobalt source and urea according to 1:2:The mol ratio of (3-6) add water it is scattered, continue stir 1h, obtain mixed solution；
In the liner that mixed solution is poured into water heating kettle, it is then placed in homogeneous reactor, in 120 DEG C of hydro-thermal reaction 0.5-
1.5h, then by hydrothermal product in 300-400 DEG C of calcining 2-3, obtain the sour Ni cluster of three-dimensional structure micron order cobalt；
(2) three-dimensional porous activated carbon is prepared：
Citric acid and NaCl are pressed 1:60 mass ratio is dissolved in deionized water, and vacuum drying removes moisture, then in nitrogen gas
2h is calcined in 750 DEG C under atmosphere, three-dimensional porous activated carbon is obtained；
(3) ultracapacitor is prepared：
Using positive active material, binding agent and the charcoal of the sour Ni cluster of the three-dimensional structure micron order cobalt obtained comprising step (1)
It is black to prepare positive pole；
Negative pole is prepared using negative electrode active material, binding agent and the carbon black of the three-dimensional porous activated carbon obtained comprising step (2)；
Ultracapacitor is prepared into using positive pole, negative pole, barrier film and electrolyte；
In the ultracapacitor, the mass ratio of three-dimensional structure micron order cobalt acid Ni cluster and three-dimensional porous activated carbon is in 0.5-1.
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| CN107473273A (en) * | 2017-08-02 | 2017-12-15 | 东北大学秦皇岛分校 | Three-dimensional structure micron order cobalt acid Ni cluster, preparation method and the usage |
| CN108598627A (en) * | 2018-05-16 | 2018-09-28 | 东北大学秦皇岛分校 | A kind of high power capacity potassium-aeration cell |
| CN110993370A (en) * | 2019-11-22 | 2020-04-10 | 南京理工大学 | Ketjen black/NiCo2O4Preparation method of mixed super capacitor electrode material |
| CN117654231A (en) * | 2023-12-14 | 2024-03-08 | 延边大学 | Three-dimensional electrode reactor and method for treating chlorobenzene by cooperation of three-dimensional electrode reactor and persulfate |
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| US20160172120A1 (en) * | 2014-12-16 | 2016-06-16 | Korea Advanced Institute Of Science And Technology | Energy storage device based on nanocrystals including metal oxide rescaled by lithiation and supercapacitor using the same |
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| CN103606467A (en) * | 2013-11-21 | 2014-02-26 | 东华大学 | Preparation method for NiCo2O4/MnO2/AC water system asymmetric super capacitor |
| US20160172120A1 (en) * | 2014-12-16 | 2016-06-16 | Korea Advanced Institute Of Science And Technology | Energy storage device based on nanocrystals including metal oxide rescaled by lithiation and supercapacitor using the same |
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| CN107473273A (en) * | 2017-08-02 | 2017-12-15 | 东北大学秦皇岛分校 | Three-dimensional structure micron order cobalt acid Ni cluster, preparation method and the usage |
| CN108598627A (en) * | 2018-05-16 | 2018-09-28 | 东北大学秦皇岛分校 | A kind of high power capacity potassium-aeration cell |
| CN110993370A (en) * | 2019-11-22 | 2020-04-10 | 南京理工大学 | Ketjen black/NiCo2O4Preparation method of mixed super capacitor electrode material |
| CN110993370B (en) * | 2019-11-22 | 2022-02-18 | 南京理工大学 | Ketjen black/NiCo2O4Preparation method of mixed super capacitor electrode material |
| CN117654231A (en) * | 2023-12-14 | 2024-03-08 | 延边大学 | Three-dimensional electrode reactor and method for treating chlorobenzene by cooperation of three-dimensional electrode reactor and persulfate |
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