CN109911947A - A kind of NiCo2O4@NiMoO4Core-shell structure and preparation method thereof - Google Patents
A kind of NiCo2O4@NiMoO4Core-shell structure and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of NiCo2O4@NiMoO4Core-shell structure and preparation method thereof.Preparation method includes the following steps: to grow NiCo on a current collector2O4After presoma, by NiCo2O4Presoma is transformed into NiCo2O4, obtain NiCo2O4/ collector；By hydro-thermal reaction solution, NiCo2O4/ collector is put into hydro-thermal reaction device, is carried out hydro-thermal reaction, is obtained NiCo2O4@NiMoO4Presoma core-shell structure；By NiMoO4Presoma is transformed into NiMoO4, obtain NiCo2O4@NiMoO4Core-shell structure.The urea concentration of hydro-thermal reaction solution is controlled, to obtain the NiCo of setting shell thickness2O4@NiMoO4Core-shell structure.The present invention is in NiCo2O4@NiMoO4Shell thickness can be regulated and controled in the preparation process of core-shell structure in simple method.
Description
Technical field
The present invention relates to a kind of electrode material preparation technical fields, more particularly to a kind of NiCo2O4@NiMoO4Nucleocapsid knot
Structure and preparation method thereof.
Background technique
In the building block of supercapacitor, electrode material is one of important factor in order of its chemical property.Metal
Oxide is a kind of fake capacitance electrode material, has the specific capacitance higher than carbonaceous material, the stable circulation higher than conducting polymer
Property.Wherein, bimetallic oxide NiCo2O4It is cheap, it is environmental-friendly, conductivity be higher than single metal oxides NiO and
Co3O4, thus its electro-chemical activity is higher, is a kind of very promising electrode material for super capacitor.But bimetallic aoxidizes
Object NiCo2O4The structural strain generated in electrochemical reaction process will lead to capacity rapid decay, and cycle performance is deteriorated.
In the prior art, nucleocapsid heterojunction structure is integrated, by the synergistic effect of two kinds of materials of nucleocapsid and shell to the guarantor of core
Shield effect, can improve NiCo2O4Cycle performance.With NiCo2O4For core, nucleocapsid heterojunction structure is synthesized in super capacitor electrode
Pole Material Field has broad prospect of application.
The inventors found that: shell thickness will affect the chemical property of Core-shell structure material；But existing skill
Art proposes a kind of NiCo not yet2O4@NiMoO4The preparation method of core-shell structure, can be during the preparation process in simple method
Regulate and control NiMoO4The thickness of shell, and then lack the thickness by regulating and controlling shell to optimize NiCo2O4@NiMoO4Core-shell structure electricity
The means of chemical property.
Summary of the invention
In view of this, the present invention provides a kind of NiCo2O4@NiMoO4Core-shell structure and preparation method thereof, main purpose be
NiCo2O4@NiMoO4Prepared NiCo can be regulated and controled in core-shell structure preparation process in simple method2O4@NiMoO4Nucleocapsid knot
The shell thickness of structure.
In order to achieve the above objectives, present invention generally provides following technical solutions:
On the one hand, the embodiment of the present invention provides a kind of NiCo2O4@NiMoO4The preparation method of core-shell structure comprising such as
Lower step:
Step 1): NiCo is grown on a current collector2O4After presoma, by the NiCo on collector2O4Presoma is transformed into
NiCo2O4, obtain NiCo2O4/ collector；
Step 2): by hydro-thermal reaction solution, NiCo2O4/ collector is put into hydro-thermal reaction device, carries out hydro-thermal reaction,
The NiCo2O4NiCo in/collector2O4Upper growth NiMoO4Presoma nanostructure, obtains NiCo2O4@NiMoO4Presoma
Core-shell structure；
Step 3): by NiCo2O4@NiMoO4NiMoO in presoma core-shell structure4Presoma is transformed into NiMoO4, obtain
NiCo2O4@NiMoO4Core-shell structure；
Wherein, the urea concentration in the hydro-thermal reaction solution of the step 2) is controlled, to obtain setting NiMoO4Shell is thick
The NiCo of degree2O4@NiMoO4Core-shell structure.
Preferably, the urea concentration in the hydro-thermal reaction solution of the step 2) is 0.1~0.75mol/L；It is further excellent
Choosing, the urea concentration in the hydro-thermal reaction solution of the step 2) is 0.25~0.4mol/L/L.
Preferably, when the urea concentration in the hydro-thermal reaction solution of the step 2) be more than or equal to 0.1 mol/L, be less than
When 0.25mol/L, the step 3) obtains the first NiCo2O4 NiMoO4 core-shell structure；When the hydro-thermal reaction of the step 2) is molten
When urea concentration in liquid is 0.25~0.4mol/L, the step 3) obtains the 2nd NiCo2O4 NiMoO4 core-shell structure；When
When urea concentration in the hydro-thermal reaction solution of the step 2) is greater than 0.4mol/L, is less than or equal to 0.75mol/L, the step
3) the 3rd NiCo2O4 NiMoO4 core-shell structure is obtained；Wherein, the shell thickness > of the first NiCo2O4 NiMoO4 core-shell structure
The shell thickness of the 3rd NiCo2O4 NiMoO4 core-shell structure of shell thickness > of 2nd NiCo2O4 NiMoO4 core-shell structure；It is excellent
Choosing, the 3rd NiCo2O4 NiMoO4 core-shell structure of specific capacitance > of the 2nd NiCo2O4 NiMoO4 core-shell structure
The specific capacitance of the first NiCo2O4 NiMoO4 core-shell structure of specific capacitance >.
Preferably, the hydro-thermal reaction solution in the step 2) selects the mixing that solute is nickel salt, molybdate and urea molten
Liquid；Preferably, the nickel salt selects Ni (NO3)2, molybdate select Na2MoO4；Preferably, the hydro-thermal reaction of the step 2) is molten
In liquid, the molal quantity of nickel salt is 0.36~0.72mmol, the molal quantity of molybdate is 0.36~0.72mmol, the volume of water is 20
~40mL.
Preferably, in the step 2), the temperature control of the hydro-thermal reaction is 120~160 DEG C, the hydro-thermal reaction
Time control be 4~8 hours；Preferably, the hydro-thermal reaction device is autoclave.
Preferably, the step 1) includes:
Step 11): collector, hydro-thermal reaction solution are relayed in hydro-thermal reaction device, hydro-thermal reaction are carried out, in afflux
NiCo is grown on body2O4Presoma nanostructure, obtains NiCo2O4Presoma/collector；
Step 12): to the NiCo2O4Presoma/collector is cleaned, is dried；
Step 13): to the NiCo2O4Presoma/collector is heat-treated, by NiCo2O4Presoma is transformed into
NiCo2O4, obtain NiCo2O4/ collector；
Preferably, the collector selects charcoal cloth；
Preferably, the hydro-thermal reaction device in the step 11) is autoclave；
Preferably, in the step 11), the temperature of the hydro-thermal reaction is 120~160 DEG C, the hydro-thermal reaction
Time is 4~10 hours.
Preferably, the hydro-thermal reaction solution in the step 11) selects the mixing that solute is nickel salt, cobalt salt and urea molten
Liquid；Preferably, in the step 11), the nickel salt in hydro-thermal reaction solution selects Ni (NO3)2, cobalt salt select Co (NO3)2；It is excellent
Choosing, the urea concentration in the hydro-thermal reaction solution of the step 11) is 0.25~0.6mol/L；Preferably, the step 11)
Hydro-thermal reaction solution in, the molal quantity of nickel salt is 0.5~2mmol, and the molal quantity of cobalt salt is 1~4mmol, deionized water volume
For 10~40mL.
Preferably, the step 12) specifically: using water and ethyl alcohol successively to NiCo2O4Presoma/collector is surpassed
After sound cleaning repeatedly, by NiCo2O4Presoma/collector is put into baking oven and is dried；Preferably, the step 12)
In, the temperature of the drying process is 60~80 DEG C, the time of the drying process is 12~24 hours.
Preferably, the step 13) specifically: by the NiCo2O4Presoma/collector is put into tube furnace, in argon gas
It is heat-treated under protection, by NiCo2O4Presoma is transformed into NiCo2O4, obtain NiCo2O4/ collector；Preferably, the step
It is rapid 13) in, the temperature of the heat treatment is 300~400 DEG C, and the time of the heat treatment is 1~2 hour.
Preferably, the step 3) includes:
Step 31): to the NiCo2O4@NiMoO4Presoma core-shell structure is cleaned, is dried；
Step 32): to the NiCo2O4@NiMoO4Presoma core-shell structure is heat-treated, by NiMoO4Presoma turns
Become NiMoO4, obtain NiCo2O4@NiMoO4Core-shell structure；
Preferably, in the step 31), using water and ethyl alcohol successively to the NiCo2O4@NiMoO4Presoma nucleocapsid knot
Structure carries out after being cleaned by ultrasonic repeatedly, by the NiCo2O4@NiMoO4Presoma core-shell structure, which is put into baking oven, to be dried；It is preferred that
, in the step 31), the temperature of the drying process is 60~80 DEG C, and the time of drying process is 12~24 hours；
Preferably, in the step 32), growth there is into NiCo2O4@NiMoO4The collector of presoma core-shell structure is put into
It in tube furnace, is heat-treated under protection of argon gas, makes NiMoO4Presoma is changed into NiMoO4, obtain NiCo2O4@NiMoO4Core
Shell structure；Preferably, in the step 32), the temperature of the heat treatment is 400~450 DEG C, and the time of the heat treatment is 1
~2 hours.
Preferably, the NiCo obtained in the step 3)2O4@NiMoO4In core-shell structure, the NiCo2O4Pattern be
Nanowire structure, the NiMoO4Pattern be nanometer chip architecture.
On the other hand, the embodiment of the present invention provides a kind of NiCo2O4@NiMoO4Core-shell structure, wherein the NiCo2O4@
NiMoO4Core-shell structure includes collector, the NiCo for being grown in collection liquid surface2O4And it is grown in NiCo2O4Surface
NiMoO4；Preferably, the NiMoO4Shell thickness is preferably 10-20nm；
Preferably, NiCo2O4Pattern be nanowire structure, the NiMoO4Pattern be nanometer chip architecture.
Preferably, the NiCo2O4@NiMoO4Core-shell structure is by NiCo described in any of the above embodiments2O4@NiMoO4Nucleocapsid
The preparation method of structure is prepared.
Preferably, the NiCo2O4@NiMoO4Core-shell structure is used as electrode material.
Preferably, the NiCo2O4@NiMoO4Core-shell structure is used as the electrode material of supercapacitor.
Compared with prior art, NiCo of the invention2O4@NiMoO4Core-shell structure and preparation method thereof at least has following
The utility model has the advantages that
1. the NiCo of the embodiment of the present invention2O4@NiMoO4Core-shell structure and preparation method thereof, by the water for preparing shell
This simple method of concentration of urea is controlled in thermal response, to regulate and control NiMoO4Shell thickness, and then to optimize core-shell structure
Chemical property.This simple regulation method be present invention firstly provides.The present invention provides a kind of simple and easy to do, systems
The method of standby high-performance super capacitor electrode material.
2. the NiCo of the embodiment of the present invention2O4@NiMoO4Core-shell structure and preparation method thereof, by the water for preparing shell
In thermal response, the concentration of urea is controlled in 0.25~0.4mol/L, NiCo is obtained2O4@NiMoO4Core-shell structure has best
Chemical property.
3. the NiCo of the embodiment of the present invention2O4@NiMoO4Core-shell structure and preparation method thereof, does not use organic solvent, and water is made
For exclusive solvents, environmental pollution is small；Equipment is simple, and main Preparation equipment is baking oven and tube furnace, and cost is relatively low；Pass through change
The method that urea concentration regulates and controls shell thickness is simple, strong operability；Obtained core-shell structure is directly grown on collector, can
As the electrode material of self-supporting, cumbersome electrode production process is not needed；The NiCo of best shell thickness2O4@NiMoO4Nucleocapsid
Structure shows highest specific capacitance as electrode material.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention and the accompanying drawings.
Detailed description of the invention
Fig. 1 is NiCo prepared by the embodiment of the present invention2O4/ charcoal cloth and NiCo2O4@NiMoO4The X-ray light of core-shell structure
Electronic energy spectrum；Wherein, a curve is NiCo2O4The x-ray photoelectron spectroscopy figure of/charcoal cloth, b curve are NiCo2O4@NiMoO4Core
The x-ray photoelectron spectroscopy figure of shell structure.
Fig. 2 is NiCo prepared by the embodiment of the present invention2O4/ charcoal cloth and NiCo2O4@NiMoO4The scanning electron of core-shell structure
Microscope photograph；Wherein, a figure is NiCo2O4The scanning electron microscope diagram piece of/charcoal cloth；B figure is the first NiCo2O4@NiMoO4Core
The scanning electron microscope diagram piece of shell structure；C figure is the 2nd NiCo2O4@NiMoO4The scanning electron microscope diagram of core-shell structure
Piece；D figure is the 3rd NiCo2O4@NiMoO4The scanning electron microscope diagram piece of core-shell structure.
Fig. 3 is NiCo prepared by the embodiment of the present invention2O4/ charcoal cloth and NiCo2O4@NiMoO4Core-shell structure is in 20mV s-1
When cyclic voltammetry curve figure；Wherein, a curve is NiCo2O4/ charcoal cloth is in 20 mV s-1When cyclic voltammetry curve figure；B curve
For the first NiCo2O4@NiMoO4Core-shell structure is in 20mV s-1When cyclic voltammetry curve figure；C curve is the 2nd NiCo2O4@
NiMoO4Core-shell structure is in 20mV s-1When cyclic voltammetry curve figure；The 3rd NiCo of d curve2O4@NiMoO4Core-shell structure exists
20mV s-1When cyclic voltammetry curve figure.
Fig. 4 is NiCo prepared by the embodiment of the present invention2O4/ charcoal cloth and NiCo2O4@NiMoO4Core-shell structure is in 2mA cm-2
When constant current charge-discharge curve graph.Wherein, a curve is NiCo2O4/ charcoal cloth is in 2mA cm-2When constant current charge-discharge curve
Figure；B curve is the first NiCo2O4@NiMoO4Core-shell structure is in 2mA cm-2When constant current charge-discharge curve graph；C curve second
NiCo2O4@NiMoO4Core-shell structure is in 2mA cm-2When constant current charge-discharge curve graph；D curve is the 3rd NiCo2O4@NiMoO4
Core-shell structure is in 2mA cm-2When constant current charge-discharge curve graph.
Specific embodiment
It is of the invention to reach the technical means and efficacy that predetermined goal of the invention is taken further to illustrate, below in conjunction with
Specific embodiment, structure, feature and its effect applied according to the present invention is described in detail such as in attached drawing and preferred embodiment
Afterwards.In the following description, what different " embodiment " or " embodiment " referred to is not necessarily the same embodiment.In addition, one or more
Special characteristic, structure or feature in a embodiment can be combined by any suitable form.
On the one hand, the embodiment of the present invention provides a kind of NiCo2O4@NiMoO4The preparation method of core-shell structure comprising as follows
Step:
Step 1): NiCo is grown on a current collector2O4After presoma nanostructure, by the NiCo on collector2O4Forerunner
Body is transformed into NiCo2O4, obtain NiCo2O4/ collector.
Specifically, the step 1) includes the following steps:
Step 11): collector, hydro-thermal reaction solution are relayed in hydro-thermal reaction device, hydro-thermal reaction are carried out, in afflux
NiCo is grown on body2O4Presoma nanowire structure, obtains NiCo2O4Presoma/collector.
Preferably, step 11) specifically: prepare Ni (NO3)2、Co(NO3)2With the mixed solution of urea, stir evenly, it will
Mixed solution is transferred in autoclave, is vertically put into the charcoal cloth (collector selects charcoal cloth) cleaned up, anti-using hydro-thermal
NiCo should be grown on charcoal cloth2O4Presoma nanostructure.Wherein, the Ni (NO3)2Molal quantity be 0.5~2mmol, Co
(NO3)2Molal quantity be 1~4mmol, the concentration of urea is 0.25~0.6mol/L, and deionized water volume is 10~40mL.Its
In, the hydrothermal temperature in the step 11) is 120~160 DEG C, and the hydro-thermal reaction time is 4~10 hours.
Step 12): to the NiCo2O4Presoma/collector is cleaned, is dried.
Preferably, step 12) specifically: using deionized water and ethyl alcohol to NiCo2O4Presoma/collector is successively ultrasonic
Cleaning repeatedly, then by the NiCo after cleaning2O4Presoma/collector, which is placed in oven and dried, to be dried.Wherein, dry
The temperature of processing is 60~80 DEG C, and the time of drying process is 12~24 hours.
Step 13): to the NiCo2O4Presoma/collector is heat-treated, by NiCo2O4Presoma is transformed into
NiCo2O4, obtain NiCo2O4/ collector.
In this step, nanowire structure is maintained, NiCo2O4NiCo in/collector2O4Pattern be nano wire.
Preferably, the step 13) specifically: by NiCo2O4(growth has NiCo to presoma/collector2O4Presoma
Charcoal cloth) it is put into tube furnace, it is heat-treated under protection of argon gas, NiCo2O4Presoma is changed into NiCo2O4。
In step 13), the temperature of heat treatment is 300~400 DEG C, and the time of heat treatment is 1~2 hour.
Step 2): by hydro-thermal reaction solution, NiCo2O4/ collector is put into hydro-thermal reaction device, carries out hydro-thermal reaction,
The NiCo2O4NiCo in/collector2O4Upper growth layer of Ni MoO4Presoma nanometer chip architecture, obtains NiCo2O4@NiMoO4
Presoma core-shell structure.
Here, the urea concentration in the hydro-thermal reaction solution of step 2) is 0.1~0.75mol/L；Preferably, the step
2) the urea concentration in hydro-thermal reaction solution is 0.25~0.4mol/L.
Preferably, it is the mixed solution of nickel salt, molybdate and urea that the hydro-thermal reaction solution in step 2), which selects solute,；It is excellent
Choosing, the nickel salt selects Ni (NO3)2, molybdate select Na2MoO4；Preferably, in the hydro-thermal reaction solution of step 2), nickel salt
Molal quantity be 0.36~0.72mmol, the molal quantity of molybdate is 0.36~0.72mmol, the volume of water is 20~40mL.
Preferably, step 2) specifically: prepare hydro-thermal reaction solution, stir evenly, be transferred in autoclave, will give birth to
Long NiCo2O4Charcoal cloth be vertically put into reaction kettle, carry out hydro-thermal reaction, in NiCo2O4Layer of Ni MoO is grown above4Presoma
Nanostructure.
Preferably, the temperature control of the hydro-thermal reaction is 120~160 DEG C, the control of time of the hydro-thermal reaction for 4~
8 hours.
In this step, the urea concentration in the hydro-thermal reaction solution of the step 2) is controlled, to obtain setting NiMoO4
The NiCo of shell thickness2O4@NiMoO4Core-shell structure.Specifically, when the urea concentration in the hydro-thermal reaction solution of step 2) is big
When being equal to 0.1mol/L, being less than 0.25mol/L, the step 3) obtains the first NiCo2O4@NiMoO4Core-shell structure.Work as step
2) when the urea concentration in hydro-thermal reaction solution is 0.25~0.4mol/L, the step 3) obtains the 2nd NiCo2O4@
NiMoO4Core-shell structure.When the urea concentration in the hydro-thermal reaction solution of the step 2) be greater than 0.4mol/L, be less than or equal to
When 0.75mol/L, the step 3) obtains the 3rd NiCo2O4@NiMoO4Core-shell structure.Wherein, the first NiCo2O4@NiMoO4Core
The 2nd NiCo of shell thickness > of shell structure2O4@NiMoO4The 3rd NiCo of shell thickness > of core-shell structure2O4@NiMoO44 cores
The shell thickness of shell structure.2nd NiCo2O4@NiMoO4The 3rd NiCo of specific capacitance > of core-shell structure2O4@NiMoO4Nucleocapsid
The first NiCo of specific capacitance > of structure2O4@NiMoO4The specific capacitance of core-shell structure.
Step 3): by NiCo2O4@NiMoO4NiMoO in presoma core-shell structure4Presoma is transformed into NiMoO4, obtain
NiCo2O4@NiMoO4Core-shell structure.
During step 3), the nanometer sheet pattern of shell is made to be maintained.
Specifically, the step 3) includes:
Step 31): to the NiCo2O4@NiMoO4Presoma core-shell structure is cleaned, is dried.
Preferably, step 31) specifically: using water and ethyl alcohol successively to the NiCo2O4@NiMoO4Presoma nucleocapsid knot
Structure carries out after being cleaned by ultrasonic repeatedly, by the NiCo2O4@NiMoO4Presoma core-shell structure, which is put into baking oven, to be dried；It is preferred that
, in the step 31), the temperature of the drying process is 60~80 DEG C, and the time of drying process is 12~24 hours.
Step 32): to the NiCo2O4@NiMoO4Presoma core-shell structure is heat-treated, by NiMoO4Presoma turns
Become NiMoO4, obtain NiCo2O4@NiMoO4Core-shell structure.
Preferably, in step 32), growth there is into NiCo2O4@NiMoO4The collector of presoma core-shell structure is put into tubular type
It in furnace, is heat-treated under protection of argon gas, makes NiMoO4Presoma is changed into NiMoO4, obtain NiCo2O4@NiMoO4Nucleocapsid
Structure；Preferably, in the step 32), the temperature of the heat treatment is 400~450 DEG C, and the time of the heat treatment is 1~2
Hour.
On the other hand, present invention implementation also provides a kind of NiCo2O4@NiMoO4Core-shell structure, wherein the NiCo2O4@
NiMoO4Core-shell structure is by NiCo described in any of the above embodiments2O4@NiMoO4The preparation method of core-shell structure is prepared.Institute
The NiCo prepared2O4@NiMoO4In core-shell structure, the stratum nucleare NiCo2O4Pattern be nanowire structure, the shell
NiMoO4Pattern be nanometer chip architecture.Preferably, the NiCo2O4@NiMoO4Core-shell structure is used as electrode material；Preferably,
The NiCo2O4@NiMoO4Core-shell structure is used as the electrode material of supercapacitor.
The present invention is further illustrated below by specific experiment embodiment.
Embodiment 1
Step 1) is by the hydro-thermal reaction solution (ingredient of the hydro-thermal reaction solution are as follows: 0.5mmol Ni (NO3)2+1mmol Co
(NO3)2+ 2.5mmol urea+10mL deionized water) it pours into autoclave, and charcoal cloth is immersed in the hydro-thermal reaction solution
In.Reaction kettle sealing, which is placed in baking oven, carries out hydro-thermal reaction, and the temperature of hydro-thermal reaction is 160 DEG C, and the time of hydro-thermal reaction is 4
Hour, obtain the NiCo for the nanometer threadiness for being grown in charcoal cloth surface2O4Presoma is (that is, NiCo2O4Presoma/charcoal cloth).Spend from
Sub- water and ethyl alcohol are to NiCo2O4It after presoma/charcoal cloth cleans 3 times, dries in an oven, drying temperature is 60 DEG C, and drying time is
24 hours.By the NiCo after drying2O4Presoma/charcoal cloth is put into tube furnace, is heat-treated under protection of argon gas, heat treatment
Temperature be 300 DEG C, time of heat treatment is 2 hours, makes nanometer threadiness NiCo2O4Presoma is changed into nanometer threadiness
NiCo2O4, obtain NiCo2O4/ charcoal cloth.
Step 2) is by the hydro-thermal reaction solution (ingredient of the hydro-thermal reaction solution are as follows: 0.36mmol Ni (NO3)2+0.36mmol
Na2MoO4+ 7.5mmol urea+20mL deionized water；The concentration of urea is 0.375mol/L) it pours into reaction kettle；Again will
NiCo2O4/ charcoal cloth is vertically impregnated in the hydro-thermal reaction solution.Reaction kettle sealing, which is placed in baking oven, carries out hydro-thermal reaction, hydro-thermal
Reaction temperature is 120 DEG C, and the time of hydro-thermal reaction is 4 hours, obtains the NiCo for being grown in charcoal cloth surface2O4@NiMoO4Presoma
Core-shell structure.Here, the pattern of NiMoO4 presoma is nano-sheet.
Step 3) deionized water and ethyl alcohol are to NiCo2O4@NiMoO4After presoma core-shell structure cleans 3 times, in baking oven
In be dried；Wherein, the temperature of drying process is 80 DEG C, the time is 12 hours.By the NiCo after drying2O4@
NiMoO4Presoma core-shell structure is placed in tube furnace, is heat-treated under protection of argon gas, and heat treatment temperature is 430 DEG C, heat
The time of processing is 1.5 hours, by NiMoO4Presoma is changed into NiMoO4, NiCo2O4It is mutually constant, obtain the 2nd NiCo2O4@
NiMoO4Core-shell structure.Wherein, the 2nd NiCo2O4@NiMoO4In core-shell structure, stratum nucleare NiCo2O4Pattern be nanowire structure,
Shell NiMoO4Pattern be nanometer chip architecture
Chemical property is tested using three electrodes.6M KOH is as electrolyte, and platinized platinum is as auxiliary electrode, mercury/oxygen
Change mercury as reference electrode, gained NiCo2O4/ charcoal cloth, NiCo2O4@NiMoO4Core-shell structure is as working electrode.
Embodiment 2
Step 1) is by the hydro-thermal reaction solution (ingredient of the hydro-thermal reaction solution are as follows: 1mmol Ni (NO3)2+2 mmol Co
(NO3)2+ 10mmol urea+20mL deionized water) it pours into autoclave, and charcoal cloth is immersed in the hydro-thermal reaction solution
In.Reaction kettle sealing, which is placed in baking oven, carries out hydro-thermal reaction, and the temperature of hydro-thermal reaction is 140 DEG C, and the time of hydro-thermal reaction is 8
Hour, obtain the NiCo for the nanometer threadiness for being grown in charcoal cloth surface2O4Presoma is (that is, NiCo2O4Presoma/charcoal cloth).Spend from
Sub- water and ethyl alcohol are to NiCo2O4It after presoma/charcoal cloth cleans 3 times, dries in an oven, drying temperature is 80 DEG C, and drying time is
12 hours.By the NiCo after drying2O4Presoma/charcoal cloth is put into tube furnace, is heat-treated under protection of argon gas, heat treatment
Temperature be 400 DEG C, time of heat treatment is 1 hour, makes nanometer threadiness NiCo2O4Presoma is changed into nanometer threadiness
NiCo2O4, obtain NiCo2O4/ charcoal cloth.
Step 2) is by the hydro-thermal reaction solution (ingredient of the hydro-thermal reaction solution are as follows: 0.72mmol Ni (NO3)2+0.72mmol
Na2MoO4+ 30mmol urea+40mL deionized water；The concentration of urea is 0.75mol/L) it pours into reaction kettle；Again will
NiCo2O4/ charcoal cloth is vertically impregnated in the hydro-thermal reaction solution.Reaction kettle sealing, which is placed in baking oven, carries out hydro-thermal reaction, hydro-thermal
Reaction temperature is 120 DEG C, and the time of hydro-thermal reaction is 4 hours, obtains the NiCo for being grown in charcoal cloth surface2O4@NiMoO4Presoma
Core-shell structure.Here, NiMoO4The pattern of presoma is nano-sheet.
Step 3) deionized water and ethyl alcohol are to NiCo2O4@NiMoO4After presoma core-shell structure cleans 3 times, in baking oven
In be dried；Wherein, the temperature of drying process is 70 DEG C, the time is 20 hours.By the NiCo after drying2O4@
NiMoO4Presoma core-shell structure is placed in tube furnace, is heat-treated under protection of argon gas, and heat treatment temperature is 400 DEG C, heat
The time of processing is 2 hours, by NiMoO4Presoma is changed into NiMoO4, NiCo2O4It is mutually constant, obtain the 3rd NiCo2O4@
NiMoO4Core-shell structure.Wherein, the 3rd NiCo2O4@NiMoO4In core-shell structure, stratum nucleare NiCo2O4Pattern be nanowire structure,
Shell NiMoO4Pattern be nanometer chip architecture
Chemical property is tested using three electrodes.6M KOH is as electrolyte, and platinized platinum is as auxiliary electrode, mercury/oxygen
Change mercury as reference electrode, gained NiCo2O4/ charcoal cloth, NiCo2O4@NiMoO4Core-shell structure is as working electrode.
Embodiment 3
Step 1) is by the hydro-thermal reaction solution (ingredient of the hydro-thermal reaction solution are as follows: 2mmol Ni (NO3)2+4 mmol Co
(NO3)2+ 24mmol urea+40mL deionized water) it pours into autoclave, and charcoal cloth is immersed in the hydro-thermal reaction solution
In.Reaction kettle sealing is placed in baking oven and carries out hydro-thermal reaction, and the temperature of hydro-thermal reaction is 120 DEG C, and the time of hydro-thermal reaction is
10 hours, obtain the NiCo for the nanometer threadiness for being grown in charcoal cloth surface2O4Presoma is (that is, NiCo2O4Presoma/charcoal cloth).It spends
Ionized water and ethyl alcohol are to NiCo2O4It after presoma/charcoal cloth cleans 3 times, dries in an oven, drying temperature is 70 DEG C, drying time
It is 20 hours.By the NiCo after drying2O4Presoma/charcoal cloth is put into tube furnace, is heat-treated under protection of argon gas, at heat
The temperature of reason is 350 DEG C, and the time of heat treatment is 1.5 hours, makes nanometer threadiness NiCo2O4Presoma is changed into nanometer threadiness
NiCo2O4, obtain NiCo2O4/ charcoal cloth.
Step 2) is by the hydro-thermal reaction solution (ingredient of the hydro-thermal reaction solution are as follows: 0.54mmol Ni (NO3)2+0.54mmol
Na2MoO4+ 3mmol urea+30mL deionized water；The concentration of urea is 0.1mol/L) it pours into reaction kettle；Again by NiCo2O4/
Charcoal cloth is vertically impregnated in the hydro-thermal reaction solution.Reaction kettle sealing, which is placed in baking oven, carries out hydro-thermal reaction, hydro-thermal reaction temperature
Degree is 120 DEG C, and the time of hydro-thermal reaction is 4 hours, obtains the NiCo for being grown in charcoal cloth surface2O4@NiMoO4Presoma nucleocapsid knot
Structure.Here, NiMoO4The pattern of presoma is nano-sheet.
Step 3) deionized water and ethyl alcohol are to NiCo2O4@NiMoO4After presoma core-shell structure cleans 3 times, in baking oven
In be dried；Wherein, the temperature of drying process is 60 DEG C, the time is 24 hours.By the NiCo after drying2O4@
NiMoO4Presoma core-shell structure is placed in tube furnace, is heat-treated under protection of argon gas, and heat treatment temperature is 450 DEG C, heat
The time of processing is 1 hour, by NiMoO4Presoma is changed into NiMoO4, NiCo2O4It is mutually constant, obtain the first NiCo2O4@
NiMoO4Core-shell structure.Wherein, the first NiCo2O4@NiMoO4In core-shell structure, stratum nucleare NiCo2O4Pattern be nanowire structure,
Shell NiMoO4Pattern be nanometer chip architecture
Chemical property is tested using three electrodes.6M KOH is as electrolyte, and platinized platinum is as auxiliary electrode, mercury/oxygen
Change mercury as reference electrode, gained NiCo2O4/ charcoal cloth, NiCo2O4@NiMoO4Core-shell structure is as working electrode.
Prepared NiCo through the foregoing embodiment2O4/ charcoal cloth, the first NiCo2O4@NiMoO4Core-shell structure (3 institute of embodiment
The concentration of urea is 0.1mol/L), the 2nd NiCo in hydro-thermal reaction solution in preparation, step 22O4@NiMoO4Core-shell structure is (real
It applies prepared by example 1, the concentration of urea is 0.25-0.4mol/L), the 3rd NiCo in hydro-thermal reaction solution in step 22O4@NiMoO4
Core-shell structure (prepared by embodiment 2, the concentration of urea is 0.75mol/L in hydro-thermal reaction solution in step 2) carries out test knot
Structure is analyzed as follows:
1. in a hydro-thermal reaction in the hydro-thermal reaction of (step 1)), change urea concentration to NiCo2O4Nano wire
Pattern influences little.But in secondary hydro-thermal reaction in the hydro-thermal reaction of (step 2)), it is available not to change urea concentration
With the NiMoO of shell thickness4Nanometer sheet.
2. as can be seen from Figure 1: with NiCo2O4/ charcoal cloth is compared, NiCo2O4@NiMoO4There are Mo in core-shell structure6+, knot
The peak position proof for closing Ni and Co forms NiCo2O4And NiMoO4。
3. as can be seen from Figure 2: the hydro-thermal reaction solution in secondary hydro-thermal reaction solution (step 2)) in urea it is dense
When degree is 0.1mol/L, thicker NiMoO is obtained4Nanometer sheet；When urea concentration is 0.25~0.4mol/L, obtain relatively thin
NiMoO4Nanometer sheet；When urea concentration is 0.75 mol/L, thinner NiMoO is obtained4Nanometer sheet.That is, the first NiCo2O4@
NiMoO4The 2nd NiCo of shell thickness > of core-shell structure2O4@NiMoO4The 3rd NiCo of shell thickness > of core-shell structure2O4@
NiMoO4The shell thickness of core-shell structure.
4. as can be seen from Figure 3: cyclic voltammetry curve surround the area: relatively thin shell NiCo2O4@NiMoO4Core-shell structure ﹥
More shell layer NiCo2O4@NiMoO4Core-shell structure ﹥ thickness shell NiCo2O4@NiMoO4Core-shell structure ﹥ NiCo2O4/ charcoal cloth, explanation are worked as
The NiCo for the relatively thin shell thickness that urea concentration obtains when being 0.25~0.4 mol/L2O4@NiMoO4The ratio of core-shell structure electrode
Capacitor highest.That is, the 2nd NiCo2O4@NiMoO4The 3rd NiCo of specific capacitance > of core-shell structure2O4@NiMoO4The ratio of core-shell structure
The first NiCo of capacitor >2O4@NiMoO4The specific capacitance of core-shell structure.
5. from fig. 4, it can be seen that discharge time: relatively thin shell NiCo2O4@NiMoO4Core-shell structure ﹥ more shell layer
NiCo2O4@NiMoO4Core-shell structure ﹥ thickness shell NiCo2O4@NiMoO4Core-shell structure ﹥ NiCo2O4/ charcoal cloth, same explanation work as urea
The NiCo for the relatively thin shell thickness that concentration obtains when being 0.25~0.4mol/L2O4@NiMoO4Core-shell structure has highest than electricity
Hold.That is, the 2nd NiCo2O4@NiMoO4The 3rd NiCo of specific capacitance > of core-shell structure2O4@NiMoO4The specific capacitance > of core-shell structure
First NiCo2O4@NiMoO4The specific capacitance of core-shell structure.
In addition, it can be seen that, regulation urea concentration obtains the thickness of the nanometer sheet of three kinds of products from scanning electron microscope
It spends significantly different.First NiCo2O4@NiMoO4Shell thickness about 20-50nm, nanometer sheet size in core-shell structure receive for 100
Rice or so.2nd NiCo2O4@NiMoO4In core-shell structure shell with a thickness of 10 rans, nanometer sheet is big from top to end
Small to be gradually increased, end nanometer sheet size is up to 150 rans.3rd NiCo2O4@NiMoO4The shell thickness of core-shell structure
It is difficult with scanning electron microscope as can be seen that estimating in Nano grade, nanometer sheet size is 10 rans.From the d picture in Fig. 2
Illustration can see that the comparison of light and shade of nanometer sheet (shell) and nano wire (core) is distinct, illustrate there is very thin shell thickness.
To sum up, the NiCo of the embodiment of the present invention2O4@NiMoO4Core-shell structure and preparation method thereof, by preparing shell
This simple method of concentration of urea is controlled in hydro-thermal reaction, to regulate and control NiMoO4Shell thickness, and then to optimize nucleocapsid knot
The chemical property of structure.This simple regulation method be present invention firstly provides.The present invention provides a kind of simple and easy to do,
The method for preparing high-performance super capacitor electrode material.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, according to
According to technical spirit any simple modification, equivalent change and modification to the above embodiments of the invention, this hair is still fallen within
In the range of bright technical solution.
Claims (10)
1. a kind of NiCo2O4@NiMoO4The preparation method of core-shell structure, which is characterized in that it includes the following steps:
Step 1): NiCo is grown on a current collector2O4After presoma, by the NiCo on collector2O4Presoma is transformed into
NiCo2O4, obtain NiCo2O4/ collector；
Step 2): by hydro-thermal reaction solution, NiCo2O4/ collector is put into hydro-thermal reaction device, hydro-thermal reaction is carried out, described
NiCo2O4NiCo in/collector2O4Upper growth NiMoO4Presoma obtains NiCo2O4@NiMoO4Presoma core-shell structure；
Step 3): by NiCo2O4@NiMoO4NiMoO in presoma core-shell structure4Presoma is transformed into NiMoO4, obtain
NiCo2O4@NiMoO4Core-shell structure；
Wherein, the urea concentration in the hydro-thermal reaction solution of the step 2) is controlled, to obtain setting NiMoO4Shell thickness
NiCo2O4@NiMoO4Core-shell structure.
2. NiCo according to claim 12O4@NiMoO4The preparation method of core-shell structure, which is characterized in that the step
2) the urea concentration in hydro-thermal reaction solution is 0.1~0.75mol/L；
Preferably, the urea concentration in the hydro-thermal reaction solution of the step 2) is 0.25~0.4mol/L/L.
3. NiCo according to claim 22O4@NiMoO4The preparation method of core-shell structure, which is characterized in that
When the urea concentration in the hydro-thermal reaction solution of the step 2) is more than or equal to 0.1mol/L, is less than 0.25mol/L, institute
It states step 3) and obtains the first NiCo2O4@NiMoO4Core-shell structure；
When the urea concentration in the hydro-thermal reaction solution of the step 2) is 0.25~0.4mol/L, the step 3) obtains the
Two NiCo2O4@NiMoO4Core-shell structure；
When the urea concentration in the hydro-thermal reaction solution of the step 2) is greater than 0.4mol/L, is less than or equal to 0.75mol/L, institute
It states step 3) and obtains the 3rd NiCo2O4@NiMoO4Core-shell structure；
Wherein, the first NiCo2O4@NiMoO4The 2nd NiCo of shell thickness > of core-shell structure2O4@NiMoO4The shell of core-shell structure
The 3rd NiCo of thickness G T.GT.GT2O4@NiMoO4The shell thickness of core-shell structure；
Preferably, the 2nd NiCo2O4@NiMoO4The 3rd NiCo of specific capacitance > of core-shell structure2O4@NiMoO4Core-shell structure
The first NiCo of specific capacitance >2O4@NiMoO4The specific capacitance of core-shell structure.
4. NiCo according to claim 1-32O4@NiMoO4The preparation method of core-shell structure, which is characterized in that
It is the mixed solution of nickel salt, molybdate and urea that hydro-thermal reaction solution in the step 2), which selects solute,；Preferably, the step
In rapid hydro-thermal reaction solution 2), the molal quantity of nickel salt is 0.36~0.72mmol, the molal quantity of molybdate be 0.36~
0.72mmol, water volume be 20~40mL；Preferably, the nickel salt selects Ni (NO3)2, molybdate select Na2MoO4；
And/or
In the step 2), the temperature control of the hydro-thermal reaction is 120~160 DEG C, and the time of the hydro-thermal reaction controls
It is 4~8 hours；Preferably, the hydro-thermal reaction device is autoclave.
5. NiCo according to claim 12O4@NiMoO4The preparation method of core-shell structure, which is characterized in that the step
1) include:
Step 11): collector, hydro-thermal reaction solution are relayed in hydro-thermal reaction device, carry out hydro-thermal reaction, on a current collector
Grow NiCo2O4Presoma nanostructure, obtains NiCo2O4Presoma/collector；
Step 12): to the NiCo2O4Presoma/collector is cleaned, is dried；
Step 13): to the NiCo2O4Presoma/collector is heat-treated, by NiCo2O4Presoma is transformed into NiCo2O4,
Obtain NiCo2O4/ collector；
Preferably, the collector selects charcoal cloth；
Preferably, the hydro-thermal reaction device in the step 11) is autoclave；
Preferably, in the step 11), the temperature of the hydro-thermal reaction is 120~160 DEG C, the time of the hydro-thermal reaction
It is 4~10 hours.
6. NiCo according to claim 52O4@NiMoO4The preparation method of core-shell structure, which is characterized in that the step
11) it is the mixed solution of nickel salt, cobalt salt and urea that the hydro-thermal reaction solution in, which selects solute,；
Preferably, in the step 11), the nickel salt in hydro-thermal reaction solution selects Ni (NO3)2, cobalt salt select Co (NO3)2；
Preferably, the urea concentration in the hydro-thermal reaction solution of the step 11) is 0.25~0.6mol/L；
Preferably, in the hydro-thermal reaction solution of the step 11), the molal quantity of nickel salt is 0.5~2mmol, the molal quantity of cobalt salt
For 1~4mmol, deionized water volume is 10~40mL.
7. NiCo according to claim 52O4@NiMoO4The preparation method of core-shell structure, which is characterized in that the step
12) specifically: using water and ethyl alcohol successively to NiCo2O4Presoma/collector carries out after being cleaned by ultrasonic repeatedly, by NiCo2O4Before
Body/collector is driven to be put into baking oven and be dried；Preferably, in the step 12), the temperature of the drying process is 60
~80 DEG C, time of the drying process be 12~24 hours；And/or
The step 13) specifically: by the NiCo2O4Presoma/collector is put into tube furnace, is carried out under protection of argon gas
Heat treatment, by NiCo2O4Presoma is transformed into NiCo2O4, obtain NiCo2O4/ collector；Preferably, in the step 13), institute
The temperature for stating heat treatment is 300~400 DEG C, and the time of the heat treatment is 1~2 hour.
8. NiCo according to claim 12O4@NiMoO4The preparation method of core-shell structure, which is characterized in that the step
3) include:
Step 31): to the NiCo2O4@NiMoO4Presoma core-shell structure is cleaned, is dried；
Step 32): to the NiCo2O4@NiMoO4Presoma core-shell structure is heat-treated, by NiMoO4Presoma is transformed into
NiMoO4, obtain NiCo2O4@NiMoO4Core-shell structure；
Preferably, in the step 31), using water and ethyl alcohol successively to the NiCo2O4@NiMoO4Presoma core-shell structure into
After row ultrasonic cleaning repeatedly, by the NiCo2O4@NiMoO4Presoma core-shell structure, which is put into baking oven, to be dried；Preferably,
In the step 31), the temperature of the drying process is 60~80 DEG C, and the time of drying process is 12~24 hours；
Preferably, in the step 32), growth there is into NiCo2O4@NiMoO4The collector of presoma core-shell structure is put into tubular type
It in furnace, is heat-treated under protection of argon gas, makes NiMoO4Presoma is changed into NiMoO4, obtain NiCo2O4@NiMoO4Nucleocapsid knot
Structure；Preferably, in the step 32), the temperature of the heat treatment is 400~450 DEG C, and the time of the heat treatment is 1~2 small
When.
9. NiCo according to claim 1-82O4@NiMoO4The preparation method of core-shell structure, which is characterized in that
In the NiCo that the step 3) obtains2O4@NiMoO4In core-shell structure, NiCo2O4The pattern of stratum nucleare is nanowire structure, NiMoO4
The pattern of shell is nanometer chip architecture.
10. a kind of NiCo2O4@NiMoO4Core-shell structure, which is characterized in that the NiCo2O4@NiMoO4Core-shell structure includes afflux
Body, the NiCo for being grown in collection liquid surface2O4And it is grown in NiCo2O4The NiMoO on surface4；
Preferably, the NiMoO4Shell thickness is preferably 10-20nm；
Preferably, the NiCo2O4Pattern be nanowire structure, the NiMoO4Pattern be nanometer chip architecture；
Preferably, the NiCo2O4@NiMoO4Core-shell structure is by the described in any item NiCo of claim 1-92O4@NiMoO4Core
The preparation method of shell structure is prepared；
Preferably, the NiCo2O4@NiMoO4Core-shell structure is used as electrode material；
Preferably, the NiCo2O4@NiMoO4Core-shell structure is used as the electrode material of supercapacitor.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113089014A (en) * | 2021-04-07 | 2021-07-09 | 西南石油大学 | Super-hydrophilic super-gas-dredging efficient hydrogen evolution catalyst with core-shell structure and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107068415A (en) * | 2017-04-21 | 2017-08-18 | 河南新太行电源股份有限公司 | The preparation and application of a kind of sour nickel composite material of core shell structure nickel molybdate@cobalts |
| CN107591251A (en) * | 2017-07-14 | 2018-01-16 | 电子科技大学 | A kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material and preparation method thereof |
-
2019
- 2019-02-22 CN CN201910133442.6A patent/CN109911947B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107068415A (en) * | 2017-04-21 | 2017-08-18 | 河南新太行电源股份有限公司 | The preparation and application of a kind of sour nickel composite material of core shell structure nickel molybdate@cobalts |
| CN107591251A (en) * | 2017-07-14 | 2018-01-16 | 电子科技大学 | A kind of soap-free emulsion polymeization formulation NiCo2O4@NiMoO4Core-shell nano chip arrays material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LIANG HUANG等: "Hierarchical core-shell NiCo2O4@NiMoO4 nanowires grown on carbon cloth as integrated electrode for high-performance supercapacitors", 《NATURE》 * |
| SATYAJIT RATHA等: "Urea-Assisted Room Temperature Stabilized Metastable β‑NiMoO4: Experimental and Theoretical Insights into its Unique Bifunctional Activity toward Oxygen Evolution and Supercapacitor", 《ACS APPLIED MATERIALS & INTERFACES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113089014A (en) * | 2021-04-07 | 2021-07-09 | 西南石油大学 | Super-hydrophilic super-gas-dredging efficient hydrogen evolution catalyst with core-shell structure and preparation method thereof |
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