CN109616331A - A kind of hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material and preparation method thereof - Google Patents
A kind of hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material and preparation method thereof Download PDFInfo
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- CN109616331A CN109616331A CN201811344861.6A CN201811344861A CN109616331A CN 109616331 A CN109616331 A CN 109616331A CN 201811344861 A CN201811344861 A CN 201811344861A CN 109616331 A CN109616331 A CN 109616331A
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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
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of nickel hydroxide nano that nano flower is hud typed piece/manganese cobalt/cobalt oxide combination electrode materials and preparation method thereof.The hud typed nickel hydroxide nano piece of the nano flower/manganese cobalt/cobalt oxide combination electrode material, is with MnCo2O4.5Nano flower is core, nickel hydroxide nano piece is equably grown on the surface thereof, to prepare with very high specific capacity, stable charge/discharge, the hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material of nano flower without binder and conductive agent, it can be used for supercapacitor field, preparation process is simple, easy to operate, and repeatability is high.
Description
Technical field
The invention belongs to super capacitor material synthesis technical field, be related to a kind of hud typed nickel hydroxide nano piece/
Manganese cobalt/cobalt oxide combination electrode material and preparation method thereof.
Background technique
In recent years, the specific capacity of supercapacitor Yin Qigao, high power density, the cycle life of length, Portable small, height
The advantages that safety and be extensively studied.However in specific capacity, power density, stability and the energy for improving supercapacitor
Certain achievement is achieved on the energy-storage properties such as density.But due to the progress of the high speed development of society and demand, present people
Increasingly higher demands are proposed to running high efficiency, safety and the intelligence etc. of electronic equipment, and supercapacitor
As one of main energy device, supercapacitor is generally divided into three kinds of classes based on energy storage mechanism and electrode material property
Type: (1) electrochemical double layer capacitor, wherein storage electron adsorption desorption (pure electrostatic process)；(2) based on different faraday's electricity
Redox reaction in electrode surface occurs for container charge-storage mechanism；(3) gather the mixed capacitor of two kinds of mechanism.But
It is that the capacitor energy density of electric double layer is low, in contrast, faraday's capacitor material is due to electric double layer material.
The key factor for influencing capacitor performance is: electrode material, with the matched electrolyte of electrode material and collector, every
Film and encapsulation preparation process etc..Wherein, electrode material is the key that supercapacitor, and the weight of supercapacitor research at present
Point.Carbon-based material, metal oxide materials and conducting polymer materials are the most widely used electrode materials of three classes most study.
Wherein, since that the oxidation/reduction reaction of Rapid reversible, intercalation/deintercalation can occur in electrochemical environment is anti-for metal oxide
It answers or absorption/desorption reaction, this reaction is the principal mode of fake capacitance storage/release energy, therefore pseudocapacitors theory can deposit
The energy of storage is ten times of double layer capacitor or more, thus its hot spot for becoming capacitor area research now.From active matter
From the point of view of matter is as the chief component of electrode material, the research of transition metal oxide and its hydroxide (nickel manganese cobalt) is even more
The most important thing.
Nickel hydroxide is concerned compared to carbon based material due to possessing higher specific capacitance, but nickel hydroxide from
Son diffusion and resistance hinder its use for doing electrode material, still need to solve this problem, reduced thickness size is to be effectively reduced
Ion diffusional resistance improves capacitive property.
Prior art CN201810345079.X provides a kind of combination electrode material preparation method, including following preparation step
It is rapid: soluble divalent nickel salt, soluble divalent cobalt, hexa, lanthanum manganate and solvent being mixed, mixed liquor is obtained；
Nickel foam is added in mixed liquor after carrying out hydro-thermal reaction and obtains presoma；Presoma is successively dried, anneals and is answered
Composite electrode material.The present invention grows core-shell nano floral structure in conductive substrates nickel foam, is directly used as electrode, avoids biography
The use of conductive agent and binder, reduces additional contact resistance, passes through NiCo in system cladding process2O4And LaMnO3Collaboration
Effect, widens potential window, improves the energy density of supercapacitor.
It is multiple that prior art CN201711481492.0 discloses a kind of polyacrylonitrile/molybdenum disulfide for supercapacitor
The preparation method of condensation material.By Sodium Molybdate Dihydrate (Na2MoO4·2H2O), thiocarbamide (CH4N2S) with polymethyl methacrylate/poly-
Acrylonitrile (PMMA/PAN) core-shell structure is uniformly mixed, and the high temperature cabonization after hydro-thermal reaction obtains MoS2/PAN composite material.
Preparation method disclosed by the invention forms the PAN hollow spheres structure with uniform macropore using PMMA as template, and in PAN
Surface grows MoS2 nano flower, has not only facilitated transporting for electrolyte ion, but also have higher specific surface area, advantageously forms double electricity
Layer.
Prior art CN201310443177.4 discloses one kind and contains MnCo2O4.5Electrode material for super capacitor
Preparation method.The MnCo that method of the invention obtains2O4.5As the electrode material of supercapacitor, not only raw material rich reserves
It is easy to get, it is cheap, and also super capacitor performance is high, big high rate performance number, stable cycle performance.
In addition, nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode still not hud typed about nano flower-like at present
The report of material.
Summary of the invention
An object of the present invention is to solve that above-mentioned manganese cobalt/cobalt oxide capacitance is low, cyclical stability is poor etc. to ask
Topic and the hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material of a kind of nano flower proposed.The nano flower core
The nickel hydroxide nano piece of shell mould/manganese cobalt/cobalt oxide composite material has higher specific surface area and electric conductivity, when as electricity
When container electrode material, capacitance and stable charge/discharge with higher can be applied and electrode of super capacitor field.
The second object of the present invention is to provide the hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxides of above-mentioned one kind
The preparation method of combination electrode material is made using manganese cobalt/cobalt oxide as presoma, using ammonium fluoride as structure directing agent, nickel chloride
For nickel source, while under facilitation of the urea as exogenously added alkali, using hydro-thermal-calcining-hydro-thermal method, one kind has been prepared
The hud typed nickel hydroxide nano piece of nano flower/manganese cobalt/cobalt oxide combination electrode material, makes nickel hydroxide nano piece homoepitaxial
On manganese cobalt/cobalt oxide core, to solve MnCo2O4.5Electric conductivity is bad and is easy the problem of reuniting；On the other hand pass through hydrogen
Nickel oxide homoepitaxial is in MnCo2O4.5On, generated stable charge/discharge asks when solving it as supercapacitor
Topic.
A kind of hud typed nickel hydroxide nano piece of nano flower of the invention/manganese cobalt/cobalt oxide combination electrode material, be with
MnCo2O4.5For core, nickel hydroxide nano piece is uniformly grown at it.
The present invention also provides a kind of hud typed nickel hydroxide nano piece of above-mentioned nano flower/manganese cobalt/cobalt oxide compound electrics
Pole material, it is characterised in that；The hud typed nickel hydroxide nano piece of the nano flower/manganese cobalt/cobalt oxide combination electrode material is
With MnCo2O4.5Nano flower is core, equably grows nickel hydroxide nano piece on the surface thereof, and the nano flower is hud typed
Nickel hydroxide nano piece/the method for manganese cobalt/cobalt oxide combination electrode material as follows is prepared:
(1) by cobalt chloride hexahydrate, four chloride hydrate manganese, ammonium fluoride and urea, in deionized water, ultrasonic disperse is carried out
Uniformly (power 500-600W), to obtain mixed solution；
It in above-mentioned mixed solution, is calculated by every liter, component and content are as follows:
(2) step (1) obtained mixed solution is transferred in water heating kettle, being then placed in length is 10mm × 50mm foam
Nickel, in 100~140 DEG C of hydro-thermal reaction 6h, obtained nickel foam is rinsed several times by dehydrated alcohol and deionized water, then uses nitrogen
The drying of gas air-flow, 70 DEG C are dried in vacuo 12 hours；
(3) nickel foam prepared by step (2) is put into Muffle furnace, it is negative to get arriving in 300-350 DEG C of 1~3h of calcining
Carry MnCo2O4.5Nickel foam；
(4) the resulting nickel foam of step (3) is added in the mixed solution of six water nickel chlorides, ammonium fluoride, urea, is then existed
160-200 DEG C of hydro-thermal reaction 10h-16h；It is rinsed several times with dehydrated alcohol and its ionized water then, then is blown with stream of nitrogen gas
It is dry, and in 70 DEG C of vacuum drying 12h, to prepare the hud typed nickel hydroxide nano piece of nano flower/manganese cobalt/cobalt oxide compound electric
Pole material；
It in above-mentioned mixed solution, is calculated by every liter, component and content are as follows:
As a preferred technical solution of the present invention, mixed solution that preparation process step (1) and step (4) obtain
In, it is calculated by every liter, constituent content is as follows:
It in step (1) in mixed solution, is calculated by every liter, constituent content is as follows:
It in step (4) in mixed solution, is calculated by every liter, constituent content is as follows:
As a preferred technical solution of the present invention, mixed solution that preparation process step (1) and step (4) obtain
In, it is calculated by every liter, constituent content is as follows:
It in step (1) in mixed solution, is calculated by every liter, constituent content is as follows:
It in step (4) in mixed solution, is calculated by every liter, constituent content is as follows:
As a preferred technical solution of the present invention, mixed solution that preparation process step (1) and step (4) obtain
In, it is calculated by every liter, constituent content is as follows:
It in step (1) in mixed solution, is calculated by every liter, constituent content is as follows:
It in step (4) in mixed solution, is calculated by every liter, constituent content is as follows:
As a preferred technical solution of the present invention, mixed solution that preparation process step (1) and step (4) obtain
In, it is calculated by every liter, constituent content is as follows:
It in step (1) in mixed solution, is calculated by every liter, constituent content is as follows:
It in step (4) in mixed solution, is calculated by every liter, constituent content is as follows:
As a preferred technical solution of the present invention, the preparation method includes the following steps:
(1) CoCL2 6H2O, manganese chloride, ammonium fluoride and urea are mixed, and ultrasonic disperse is equal in deionized water
It is even, to obtain mixed solution；
(2) step (1) obtained mixed solution is transferred in water heating kettle, is then placed in 10mm × 50mm nickel foam, and
It in 100-140 DEG C of hydro-thermal reaction 6h, rinses several times using dehydrated alcohol and deionized water, and is dried up with stream of nitrogen gas, carried out
Vacuum drying；
(3) nickel foam prepared by step (2) is put into Muffle furnace, under conditions of air, controlled at 300-
350 DEG C, 1-3h is calcined, that is, preparing load has MnCo2O4.5Nickel foam；
(4) the resulting nickel foam of step (3) is added in the mixed solution of nickel chloride, ammonium fluoride, urea, and in 160-
200 DEG C of hydro-thermal reaction 10h-16h, then rinsed several times with dehydrated alcohol and its ionized water, then dried up with stream of nitrogen gas, finally 70
DEG C vacuum drying 12h, to prepare the hud typed nickel hydroxide nano piece of nano flower/manganese cobalt/cobalt oxide combination electrode material.
Compared with the prior art, the beneficial effects of the invention include:
A kind of above-mentioned resulting nickel hydroxide nano that nano flower is hud typed piece/manganese cobalt/cobalt oxide combination electrode material, by
In having obtained that there is very high specific capacity, stable charge/discharge, the hud typed hydrogen-oxygen of nano flower without binder and conductive agent
Change nickel nano film/manganese cobalt/cobalt oxide combination electrode material, can be used for electrode material for super capacitor.
A kind of hud typed nickel hydroxide nano piece of nano flower of the invention/manganese cobalt/cobalt oxide combination electrode material prepares work
Skill is simple, easy to operate, and repeatability is high.
A kind of hud typed nickel hydroxide nano piece of nano flower of the invention/manganese cobalt/cobalt oxide combination electrode material, due to
It is MnCo2O4.5Structure is nanometer flower structure, and nickel hydroxide nano piece is homoepitaxial on core, serious group does not occur
Poly- phenomenon, and it is uniform in size, material integrally has good electric conductivity.
Further, the hud typed nickel hydroxide nano piece of nano flower of the invention/manganese cobalt/cobalt oxide combination electrode material, by
MnCo is uniformly adhered in nickel hydroxide nano nanometer sheet2O4.5On nanometer flower structure, MnCo is greatly weakened2O4.5Occur
Agglomeration, nano flower do not have apparent agglomeration, shows uniform nano flower-like, and combination electrode material has good
Electric conductivity and nanometer sheet between gap, the transmission rate and electron transfer rate of electrolyte is greatly facilitated, therefore,
The hud typed nickel hydroxide nano piece of nano flower of the invention/manganese cobalt/cobalt oxide combination electrode material has very high specific capacitance
With stable charge/discharge.
Further, the hud typed nickel hydroxide nano piece of nano flower of the invention/manganese cobalt/cobalt oxide combination electrode material
Preparation method, due to the hud typed nickel hydroxide nano piece/manganese cobalt oxidation of the nano flower prepared using hydro-thermal and method for calcinating
Object combination electrode material, thus preparation process have it is easy to operate, the requirement to equipment is lower, and reaction process is easy to control, right
Environmental nonpollution, repeatability is high, is suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the hud typed nickel hydroxide nano piece of the resulting nano flower of embodiment 1/manganese cobalt/cobalt oxide combination electrode material
Material, MnCo2O4.5The XRD spectrum of nano flower and the individual nickel hydroxide of comparison.
Fig. 2 is pole scanning of materials electron microscope, wherein Fig. 2 a is the resulting nano flower MnCo of embodiment 12O4.5Pole material is swept
Retouch electron microscope；Fig. 2 b is the hud typed nickel hydroxide nano piece of the resulting nano flower of embodiment 1/manganese cobalt/cobalt oxide combination electrode material
Expect scanning electron microscope (SEM) photograph.
Fig. 3 is the hud typed nickel hydroxide nano piece of the resulting nano flower of embodiment 1/manganese cobalt/cobalt oxide combination electrode material
Cyclic voltammetry curve, be followed successively by 5mV.s from the inside to surface-1-50mV.s-1。
Fig. 4 is the hud typed nickel hydroxide nano piece of the resulting nano flower of embodiment 1/manganese cobalt/cobalt oxide combination electrode material
The charging and discharging curve under different electric currents is from left to right followed successively by 20A g-1-3A g-1。
Fig. 5 is the hud typed nickel hydroxide nano piece of the resulting nano flower of embodiment 1/manganese cobalt/cobalt oxide combination electrode material
Stable circulation linearity curve.
Fig. 6 is the hud typed nickel hydroxide nano piece of the resulting nano flower of embodiment 2/manganese cobalt/cobalt oxide combination electrode material
Cyclic voltammetry curve, be followed successively by 5mV.s from the inside to surface-1-50mV.s-1。
Fig. 7 is the hud typed nickel hydroxide nano piece of the resulting nano flower of embodiment 3/manganese cobalt/cobalt oxide combination electrode material
Stable circulation linearity curve, be followed successively by 5mV.s from the inside to surface-1-60mV.s-1。
Fig. 8 is the hud typed nickel hydroxide nano piece of the resulting nano flower of embodiment 4/manganese cobalt/cobalt oxide combination electrode material
The charging and discharging curve under different electric currents is from left to right followed successively by 8A g-1-1A g-1。
Specific embodiment
The present invention is further described below by specific embodiment and in conjunction with attached drawing, but does not limit the present invention.
Embodiment 1
A kind of nickel hydroxide nano that nano flower is hud typed piece/manganese cobalt/cobalt oxide combination electrode material of the present invention, be with
MnCo2O4.5For core, in its surface homoepitaxial nickel hydroxide nano piece.
The present invention also provides a kind of hud typed nickel hydroxide nano piece of above-mentioned nano flower/manganese cobalt/cobalt oxide compound electrics
The preparation method of pole material, comprising the following steps:
(1), cobalt chloride hexahydrate, four chloride hydrate manganese, ammonium fluoride and urea are subjected to ultrasonic disperse in deionized water
Uniformly (power 500-600W) obtains mixed solution；
It in above-mentioned mixed solution, is calculated by every liter, component and content are as follows:
(2), step (1) obtained mixed solution is transferred in water heating kettle, is then placed in 10mm × 50mm nickel foam, and
It in 120 DEG C of hydro-thermal reaction 6h, rinses several times, and is dried up with stream of nitrogen gas, 70 DEG C of vacuum using dehydrated alcohol and deionized water
It is 12 hours dry；
(3), nickel foam prepared by step (2) is put into Muffle furnace, in 350 DEG C of calcining 2h, that is, preparing load has
MnCo2O4.5Nickel foam；
(4), it by step (3) resulting nickel foam, is added in the mixed solution of six water nickel chlorides, ammonium fluoride, urea, and
180 DEG C of hydro-thermal reaction 12h, then rinsed several times with dehydrated alcohol and its ionized water, and dried up with stream of nitrogen gas, it is finally true at 70 DEG C
The dry 12h of sky, to obtain the hud typed nickel hydroxide nano piece of nano flower/manganese cobalt/cobalt oxide combination electrode material；
It in above-mentioned mixed solution, is calculated by every liter, component and content are as follows:
Resulting XRD diagram is as shown in Figure 1.From figure 1 it appears that be obtained by above-mentioned preparation method pure cerium hydroxide nickel and
MnCo2O4.5Composite material, without obvious impurity peaks.
Gained scanning electron microscope (SEM) photograph, respectively as shown in Fig. 2 a, 2b.It can be seen that coming, nickel hydroxide nano piece from Fig. 2 a, 2b
Homoepitaxial is in MnCo2O4.5On nano flower；And the hud typed nickel hydroxide nano piece/manganese cobalt oxidation of prepared nano flower
Object combination electrode material has good electric conductivity, uniform core-shell structure, therefore has very big specific surface area.
Using the hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material of above-mentioned prepared nano flower as
Working electrode, is not necessarily to binder and conductive agent, capacity measurement select three-electrode system (wherein platinum plate electrode is as reference electrode,
Silver chlorate is as reference electrode), it is carried out in the KOH solution of 2M.
Using electrochemical workstation, the nickel hydroxide nano piece/manganese cobalt oxidation hud typed to above-mentioned prepared nano flower
Object combination electrode material carries out stable circulation performance test, resulting cyclic voltammetric under the sweep speed of 5~50mV/s respectively
Curve graph is as shown in Figure 3.From figure 3, it can be seen that nickel hydroxide nano piece/manganese cobalt oxidation that above-mentioned gained nano flower is hud typed
Object composite material has good cycle performance, can be applied to electrode of super capacitor field.
It is compound using the electrochemical workstation nickel hydroxide nano piece/manganese cobalt/cobalt oxide hud typed to above-mentioned gained nano flower
Charge-discharge performance of the electrode material respectively when current density is 3~20A/g is measured, resulting charging and discharging curve such as Fig. 4
It is shown.Figure 4, it is seen that nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material that above-mentioned nano flower is hud typed
Material is used as electrode material for super capacitor, has good charge-discharge performance.
It is multiple using the battery test system nickel hydroxide nano piece/manganese cobalt/cobalt oxide hud typed to above-mentioned resulting nano flower
Composite electrode material carries out cyclical stability test, as shown in Figure 5.From figure 5 it can be seen that above-mentioned resulting nano flower is hud typed
Nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material, have good cyclical stability.
Embodiment 2
A kind of nickel hydroxide nano that nano flower is hud typed piece/manganese cobalt/cobalt oxide combination electrode material of the present invention, be with
MnCo2O4.5For core, in its surface homoepitaxial nickel hydroxide nano piece.
The present invention also provides a kind of hud typed nickel hydroxide nano piece of above-mentioned nano flower/manganese cobalt/cobalt oxide compound electrics
The preparation method of pole material, comprising the following steps:
(1), cobalt chloride hexahydrate, four chloride hydrate manganese, ammonium fluoride and urea are subjected to ultrasonic disperse in deionized water
Uniformly (power 500-600W) obtains mixed solution；
It in above-mentioned mixed solution, is calculated by every liter, component and content are as follows:
(2), step (1) obtained mixed solution is transferred in water heating kettle, is then placed in 10mm × 50mm nickel foam, and
It in 140 DEG C of hydro-thermal reaction 6h, rinses several times, and is dried up with stream of nitrogen gas, 70 DEG C of vacuum using dehydrated alcohol and deionized water
It is 12 hours dry；
(3), nickel foam prepared by step (2) is put into Muffle furnace, in 350 DEG C of calcining 3h, that is, preparing load has
MnCo2O4.5Nickel foam；
(4), it by step (3) resulting nickel foam, is added in the mixed solution of six water nickel chlorides, ammonium fluoride, urea, and
200 DEG C of hydro-thermal reaction 12h, then rinsed several times with dehydrated alcohol and its ionized water, and dried up with stream of nitrogen gas, it is finally true at 70 DEG C
The dry 12h of sky, to obtain the hud typed nickel hydroxide nano piece of nano flower/manganese cobalt/cobalt oxide combination electrode material；
It in above-mentioned mixed solution, is calculated by every liter, component and content are as follows:
It is multiple using the electrochemical workstation nickel hydroxide nano piece/manganese cobalt/cobalt oxide hud typed to above-mentioned resulting nano flower
Composite electrode material carries out stable circulation performance test under 5,10,20,30,40,50mV/s sweep speed respectively, resulting to follow
Ring volt-ampere curve figure is as shown in fig. 6, from fig. 6 it can be seen that the hud typed nickel hydroxide nano piece/manganese of above-mentioned gained nano flower
Cobalt/cobalt oxide combination electrode material has cycle performance well, may be used as electrode material for super capacitor use.
Embodiment 3
A kind of nickel hydroxide nano that nano flower is hud typed piece/manganese cobalt/cobalt oxide combination electrode material of the present invention, be with
MnCo2O4.5For core, in its surface homoepitaxial nickel hydroxide nano piece.
The present invention also provides a kind of hud typed nickel hydroxide nano piece of above-mentioned nano flower/manganese cobalt/cobalt oxide compound electrics
The preparation method of pole material, comprising the following steps:
(1), by cobalt chloride hexahydrate, four chloride hydrate manganese, ammonium fluoride and urea control power in 500-600W, in room
Ultrasonic disperse is carried out uniformly in deionized water under warm ultrasound condition, obtains mixed solution；
It in above-mentioned mixed solution, is calculated by every liter, component and content are as follows:
(2), step (1) obtained mixed solution is transferred in water heating kettle and length is then added is 1*5CM nickel foam,
100 DEG C, hydro-thermal reaction is carried out under conditions of 6h, obtained nickel foam is rinsed several times by dehydrated alcohol and deionized water, then is used
Stream of nitrogen gas drying, is dried in vacuo 12 hours, and 70 degrees Celsius；
(3), nickel foam obtained by step (2) is put into Muffle furnace, under conditions of air, controlled at 300 DEG C, is forged
Burn 1h.Obtain load MnCo2O4.5Nickel foam；
(4), the resulting nickel foam of step (3) is added six water nickel chlorides, ammonium fluoride, in the mixed solution of urea, by it
It in 160 DEG C of hydro-thermal reaction 16h, obtains nickel foam and rinses it several times with dehydrated alcohol and its ionized water, then blown with stream of nitrogen gas
It is dry, it is dried in vacuo 12h, 70 DEG C, has obtained the hud typed nickel hydroxide nano piece of nano flower/manganese cobalt/cobalt oxide combination electrode material
Material；
It in above-mentioned mixed solution, is calculated by every liter, component and content are as follows:
It is multiple using the electrochemical workstation nickel hydroxide nano piece/manganese cobalt/cobalt oxide hud typed to above-mentioned resulting nano flower
Composite electrode material carries out stable circulation performance test under 5,10,20,30,40,50mV/s sweep speed respectively, resulting to follow
Ring volt-ampere curve figure is as shown in fig. 7, it can be seen from figure 7 that the hud typed nickel hydroxide nano piece/manganese of above-mentioned gained nano flower
Cobalt/cobalt oxide combination electrode material has cycle performance well, may be used as electrode material for super capacitor use.
Embodiment 4
A kind of nickel hydroxide nano that nano flower is hud typed piece/manganese cobalt/cobalt oxide combination electrode material of the present invention, be with
MnCo2O4.5For core, in its surface homoepitaxial nickel hydroxide nano piece.
The present invention also provides a kind of hud typed nickel hydroxide nano piece of above-mentioned nano flower/manganese cobalt/cobalt oxide compound electrics
The preparation method of pole material, comprising the following steps:
(1), by cobalt chloride hexahydrate, four chloride hydrate manganese, ammonium fluoride and urea control power in 500-600W, in room
Ultrasonic disperse is carried out uniformly in deionized water under warm ultrasound condition, obtains mixed solution；
It in above-mentioned mixed solution, is calculated by every liter, component and content are as follows:
(2), step (1) obtained mixed solution is transferred in water heating kettle and length is then added is 1*5CM nickel foam,
140 DEG C, hydro-thermal reaction is carried out under conditions of 6h, obtained nickel foam is rinsed several times by dehydrated alcohol and deionized water, then is used
Stream of nitrogen gas drying, is dried in vacuo 12 hours, and 70 degrees Celsius；
(3), nickel foam obtained by step (2) is put into Muffle furnace, under conditions of air, controlled at 300 DEG C, is forged
Burn 1h.Obtain load MnCo2O4.5Nickel foam；
(4), the resulting nickel foam of step (3) is added six water nickel chlorides, ammonium fluoride, in the mixed solution of urea, by it
It in 160 DEG C of hydro-thermal reaction 16h, obtains nickel foam and rinses it several times with dehydrated alcohol and its ionized water, then blown with stream of nitrogen gas
It is dry, it is dried in vacuo 12h, 70 DEG C, has obtained the hud typed nickel hydroxide nano piece of nano flower/manganese cobalt/cobalt oxide combination electrode material
Material；
It in above-mentioned mixed solution, is calculated by every liter, component and content are as follows:
It is compound using the electrochemical workstation nickel hydroxide nano piece/manganese cobalt/cobalt oxide hud typed to above-mentioned gained nano flower
The performance of charge and discharge of the electrode material respectively when current density is 1,2,3,5,8A/g is measured, resulting charging and discharging curve
As shown in figure 4, figure 4, it is seen that the hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxide compound electric of above-mentioned nano flower
Pole material has charge-discharge performance well as electrode material for super capacitor.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, several simple inferences or replacement can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (6)
1. a kind of nickel hydroxide nano that nano flower is hud typed piece/manganese cobalt/cobalt oxide combination electrode material, it is characterised in that；It is described
The hud typed nickel hydroxide nano piece/manganese cobalt/cobalt oxide combination electrode material of nano flower be with MnCo2O4.5Nano flower is core,
Nickel hydroxide nano piece, the hud typed nickel hydroxide nano piece/manganese cobalt oxide of the nano flower are equably grown on the surface thereof
The method of compound combination electrode material as follows is prepared:
(1) by cobalt chloride hexahydrate, four chloride hydrate manganese, ammonium fluoride and urea, in deionized water, carry out ultrasonic disperse it is uniform
(power 500-600W), to obtain mixed solution；
It in above-mentioned mixed solution, is calculated by every liter, component and content are as follows:
(2) step (1) obtained mixed solution is transferred in water heating kettle, being then placed in length is 10mm × 50mm nickel foam,
In 100~140 DEG C of hydro-thermal reaction 6h, obtained nickel foam is rinsed several times by dehydrated alcohol and deionized water, then uses nitrogen
Air-flow drying, 70 DEG C are dried in vacuo 12 hours；
(3) nickel foam prepared by step (2) is put into Muffle furnace, 300-350 DEG C of 1~3h of calcining to get to load
MnCo2O4.5Nickel foam；
(4) the resulting nickel foam of step (3) is added in the mixed solution of six water nickel chlorides, ammonium fluoride, urea, then in 160-
200 DEG C of hydro-thermal reaction 10h-16h；It is rinsed several times with dehydrated alcohol and its ionized water then, then is dried up with stream of nitrogen gas, and
In 70 DEG C of vacuum drying 12h, to prepare the hud typed nickel hydroxide nano piece of nano flower/manganese cobalt/cobalt oxide combination electrode material
Material；
It in above-mentioned mixed solution, is calculated by every liter, component and content are as follows:
Six water nickel chloride 0.47-0.7g
Ammonium fluoride 0.2g
Urea 0.6-1g
Surplus is deionized water.
2. a kind of nickel hydroxide nano that nano flower is hud typed piece/manganese cobalt/cobalt oxide combination electrode material as described in claim 1
Material, it is characterised in that: in the mixed solution that preparation process step (1) and step (4) obtain, calculated by every liter, constituent content
It is as follows:
It in step (1) in mixed solution, is calculated by every liter, constituent content is as follows:
It in step (4) in mixed solution, is calculated by every liter, constituent content is as follows:
Six water nickel chloride 0.47g
Ammonium fluoride 0.2g
Urea 0.6g
Surplus is deionized water.
3. a kind of nickel hydroxide nano that nano flower is hud typed piece/manganese cobalt/cobalt oxide combination electrode material as described in claim 1
Material, it is characterised in that: in the mixed solution that preparation process step (1) and step (4) obtain, calculated by every liter, constituent content
It is as follows:
It in step (1) in mixed solution, is calculated by every liter, constituent content is as follows:
It in step (4) in mixed solution, is calculated by every liter, constituent content is as follows:
Six water nickel chloride 0.7g
Ammonium fluoride 0.2g
Urea 1g
Surplus is deionized water.
4. a kind of nickel hydroxide nano that nano flower is hud typed piece/manganese cobalt/cobalt oxide combination electrode material as described in claim 1
Material, it is characterised in that: in the mixed solution that preparation process step (1) and step (4) obtain, calculated by every liter, constituent content
It is as follows:
It in step (1) in mixed solution, is calculated by every liter, constituent content is as follows:
It in step (4) in mixed solution, is calculated by every liter, constituent content is as follows:
Six water nickel chloride 0.58g
Ammonium fluoride 0.2g
Urea 0.8g
Surplus is deionized water.
5. a kind of nickel hydroxide nano that nano flower is hud typed piece/manganese cobalt/cobalt oxide combination electrode material as described in claim 1
Material, it is characterised in that: in the mixed solution that preparation process step (1) and step (4) obtain, calculated by every liter, constituent content
It is as follows:
It in step (1) in mixed solution, is calculated by every liter, constituent content is as follows:
It in step (4) in mixed solution, is calculated by every liter, constituent content is as follows:
Six water nickel chloride 0.58g
Ammonium fluoride 0.2g
Urea 1g
Surplus is deionized water.
6. a kind of nickel hydroxide nano that nano flower is hud typed piece/manganese cobalt oxide described in any claim in claim 1-5
Compound combination electrode material, which is characterized in that the preparation method includes the following steps:
(1) CoCL2 6H2O, manganese chloride, ammonium fluoride and urea are mixed, and ultrasonic disperse is uniform in deionized water, from
And obtain mixed solution；
(2) step (1) obtained mixed solution is transferred in water heating kettle, is then placed in 10mm × 50mm nickel foam, and
100-140 DEG C of hydro-thermal reaction 6h is rinsed several times using dehydrated alcohol and deionized water, and is dried up with stream of nitrogen gas, is carried out true
Sky is dry；
(3) nickel foam prepared by step (2) is put into Muffle furnace, under conditions of air, controlled at 300-350
DEG C, 1-3h is calcined, that is, preparing load has MnCo2O4.5Nickel foam；
(4) the resulting nickel foam of step (3) is added in the mixed solution of nickel chloride, ammonium fluoride, urea, and at 160-200 DEG C
Hydro-thermal reaction 10h-16h, then rinsed several times with dehydrated alcohol and its ionized water, then dried up with stream of nitrogen gas, it is finally true at 70 DEG C
The dry 12h of sky, to prepare the hud typed nickel hydroxide nano piece of nano flower/manganese cobalt/cobalt oxide combination electrode material.
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| CN114057241A (en) * | 2021-12-10 | 2022-02-18 | 福建工程学院 | Preparation method and application of self-supporting low-crystalline-phase nickel hydroxide nanosheet electrode inlaid with nickel molybdate nanoparticles |
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| CN114023568A (en) * | 2021-09-24 | 2022-02-08 | 多助科技(武汉)有限公司 | Nickel-tin alloy @ nickel hydroxide core-shell structure composite material and preparation and application thereof |
| CN114057241A (en) * | 2021-12-10 | 2022-02-18 | 福建工程学院 | Preparation method and application of self-supporting low-crystalline-phase nickel hydroxide nanosheet electrode inlaid with nickel molybdate nanoparticles |
| CN114057241B (en) * | 2021-12-10 | 2023-09-08 | 福建工程学院 | Preparation method and application of self-supporting low-crystalline-phase nickel hydroxide nanosheet electrode inlaid with nickel molybdate nanoparticles |
| CN114751369A (en) * | 2022-05-19 | 2022-07-15 | 重庆大学 | MnCo2O4.5-MgH2Composite hydrogen storage material and preparation method thereof |
| CN114751369B (en) * | 2022-05-19 | 2023-07-04 | 重庆大学 | MnCo 2 O 4.5 -MgH 2 Composite hydrogen storage material and preparation method thereof |
| CN115497745A (en) * | 2022-09-23 | 2022-12-20 | 安阳师范学院 | Flower-like multi-level structured core-shell nickel cobaltate-manganese cobaltate electrode material and preparation method thereof |
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