CN109911947B - NiCo2O4@NiMoO4Core-shell structure and preparation method thereof - Google Patents
NiCo2O4@NiMoO4Core-shell structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to NiCo2O4@NiMoO4Core-shell structures and methods of making the same. The preparation method comprises the following steps: growing NiCo on a current collector2O4After the precursor, NiCo is added2O4Conversion of precursors to NiCo2O4Obtaining NiCo2O4A current collector; mixing the hydrothermal reaction solution and NiCo2O4Putting the current collector into a hydrothermal reaction device for hydrothermal reaction to obtain NiCo2O4@NiMoO4A precursor core-shell structure; mixing NiMoO4Conversion of precursor into NiMoO4Obtaining NiCo2O4@NiMoO4A core-shell structure. Controlling the urea concentration of the hydrothermal reaction solution to obtain NiCo with set shell thickness2O4@NiMoO4A core-shell structure. The invention is in NiCo2O4@NiMoO4The thickness of the shell layer can be regulated and controlled by a simple method in the preparation process of the core-shell structure.
Description
Technical Field
The invention relates to the technical field of electrode material preparation, in particular to NiCo2O4@NiMoO4Core-shell structures and methods of making the same.
Background
In the component parts of the super capacitor, the electrode materialThe material is one of the important influencing factors of the electrochemical performance. The metal oxide is a pseudo-capacitance electrode material, has higher specific capacitance than a carbonaceous material, and has higher cycling stability than a conductive polymer. Wherein the bimetallic oxide NiCo2O4Low cost, environment friendship and conductivity higher than that of single metal oxide NiO and Co3O4Therefore, the electrochemical activity of the material is higher, and the material is a super capacitor electrode material with high potential. However, the bimetallic oxide NiCo2O4The structural strain generated during the electrochemical reaction process causes rapid capacity fade and poor cycle performance.
In the prior art, a core-shell heterostructure is integrated, and NiCo can be improved through the synergistic effect of two core-shell materials and the protection effect of a shell on a core2O4The cycle performance of (c). With NiCo2O4As a core, the synthesized core-shell heterostructure has wide application prospect in the field of electrode materials of super capacitors.
The inventors of the present invention found that: the thickness of the shell layer can influence the electrochemical performance of the core-shell structure material; however, the prior art has not proposed a NiCo2O4@NiMoO4The preparation method of the core-shell structure can regulate and control NiMoO by a simple method in the preparation process4The thickness of the shell, and hence the lack of optimization of NiCo by controlling the thickness of the shell2O4@NiMoO4Means of electrochemical performance of core-shell structure.
Disclosure of Invention
In view of the above, the present invention provides a NiCo2O4@NiMoO4A core-shell structure and a preparation method thereof, mainly aiming at NiCo2O4@NiMoO4The NiCo prepared by simple method regulation and control can be realized in the preparation process of the core-shell structure2O4@NiMoO4Shell thickness of core-shell structure.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, embodiments of the present invention provide a NiCo2O4@NiMoO4Preparation method of core-shell structureWhich comprises the following steps:
step 1): growing NiCo on a current collector2O4After the precursor, NiCo on the current collector is added2O4Conversion of precursors to NiCo2O4Obtaining NiCo2O4A current collector;
step 2): mixing the hydrothermal reaction solution and NiCo2O4Putting the current collector into a hydrothermal reaction device for hydrothermal reaction, and putting the NiCo into the reactor for hydrothermal reaction2O4NiCo in Current collector2O4Overgrowth of NiMoO4Precursor nano structure to obtain NiCo2O4@NiMoO4A precursor core-shell structure;
step 3): mixing NiCo2O4@NiMoO4NiMoO in precursor core-shell structure4Conversion of precursor into NiMoO4Obtaining NiCo2O4@NiMoO4A core-shell structure;
wherein the concentration of urea in the hydrothermal reaction solution of the step 2) is controlled to obtain the set NiMoO4NiCo with shell thickness2O4@NiMoO4A core-shell structure.
Preferably, the concentration of urea in the hydrothermal reaction solution in the step 2) is 0.1-0.75 mol/L; further preferably, the concentration of urea in the hydrothermal reaction solution in the step 2) is 0.25-0.4 mol/L/L.
Preferably, when the concentration of urea in the hydrothermal reaction solution in the step 2) is more than or equal to 0.1mol/L and less than 0.25mol/L, the step 3) obtains a first NiCo2O4@ NiMoO4 core-shell structure; when the concentration of urea in the hydrothermal reaction solution in the step 2) is 0.25-0.4mol/L, obtaining a second NiCo2O4@ NiMoO4 core-shell structure in the step 3); when the concentration of urea in the hydrothermal reaction solution in the step 2) is more than 0.4mol/L and less than or equal to 0.75mol/L, obtaining a third NiCo2O4@ NiMoO4 core-shell structure in the step 3); the shell thickness of the first NiCo2O4@ NiMoO4 core-shell structure is larger than that of the second NiCo2O4@ NiMoO4 core-shell structure is larger than that of the third NiCo2O4@ NiMoO4 core-shell structure; preferably, the specific capacitance of the second NiCo2O4@ NiMoO4 core-shell structure is larger than the specific capacitance of the third NiCo2O4@ NiMoO4 core-shell structure is larger than the specific capacitance of the first NiCo2O4@ NiMoO4 core-shell structure.
Preferably, the hydrothermal reaction solution in the step 2) is a mixed solution of nickel salt, molybdate and urea as a solute; preferably, the nickel salt is Ni (NO)3)2The molybdate is Na2MoO4(ii) a Preferably, in the hydrothermal reaction solution of step 2), the molar number of the nickel salt is 0.36 to 0.72mmol, the molar number of the molybdate is 0.36 to 0.72mmol, and the volume of water is 20 to 40 mL.
Preferably, in the step 2), the temperature of the hydrothermal reaction is controlled to be 120-160 ℃, and the time of the hydrothermal reaction is controlled to be 4-8 hours; preferably, the hydrothermal reaction device is a high-pressure reaction kettle.
Preferably, the step 1) includes:
step 11): transferring the current collector and the hydrothermal reaction solution into a hydrothermal reaction device for hydrothermal reaction, and growing NiCo on the current collector2O4Precursor nano structure to obtain NiCo2O4A precursor/current collector;
step 12): for the NiCo2O4Cleaning and drying the precursor/current collector;
step 13): for the NiCo2O4Heat treating the precursor/current collector to obtain NiCo2O4Conversion of precursors to NiCo2O4Obtaining NiCo2O4A current collector;
preferably, the current collector is made of carbon cloth;
preferably, the hydrothermal reaction device in the step 11) is a high-pressure reaction kettle;
preferably, in the step 11), the temperature of the hydrothermal reaction is 120 to 160 ℃, and the time of the hydrothermal reaction is 4 to 10 hours.
Preferably, the hydrothermal reaction solution in the step 11) is a mixed solution of nickel salt, cobalt salt and urea as a solute; preferably, in the step 11), the nickel salt in the hydrothermal reaction solution is Ni (NO)3)2Co (NO) is selected as cobalt salt3)2(ii) a Preferably, the concentration of urea in the hydrothermal reaction solution in the step 11) is 0.25-0.6 mol/L; preferably, in the hydrothermal reaction solution in the step 11), the mole number of the nickel salt is 0.5-2 mmol, the mole number of the cobalt salt is 1-4 mmol, and the volume of the deionized water is 10-40 mL.
Preferably, the step 12) is specifically: sequential treatment of NiCo with Water and ethanol2O4After the precursor/current collector is subjected to ultrasonic cleaning for multiple times, NiCo is added2O4Putting the precursor/current collector into an oven for drying treatment; preferably, in the step 12), the temperature of the drying treatment is 60 to 80 ℃, and the time of the drying treatment is 12 to 24 hours.
Preferably, the step 13) is specifically: mixing the NiCo2O4Putting the precursor/current collector into a tube furnace, carrying out heat treatment under the protection of argon, and adding NiCo2O4Conversion of precursors to NiCo2O4Obtaining NiCo2O4A current collector; preferably, in the step 13), the heat treatment temperature is 300-400 ℃, and the heat treatment time is 1-2 hours.
Preferably, the step 3) includes:
step 31): for the NiCo2O4@NiMoO4Cleaning and drying the precursor core-shell structure;
step 32): for the NiCo2O4@NiMoO4Heat treating the precursor core-shell structure to obtain NiMoO4Conversion of precursor into NiMoO4Obtaining NiCo2O4@NiMoO4A core-shell structure;
preferably, in the step 31), water and ethanol are adopted to sequentially react the NiCo2O4@NiMoO4After the precursor core-shell structure is subjected to ultrasonic cleaning for multiple times, the NiCo is subjected to ultrasonic cleaning2O4@NiMoO4Putting the precursor core-shell structure into an oven for drying; preferably, in the step 31), the temperature of the drying treatment is 60-80 ℃, and the time of the drying treatment is 12-E24 hours;
preferably, in said step 32), NiCo will be grown2O4@NiMoO4Putting the current collector with the precursor core-shell structure into a tube furnace, and carrying out heat treatment under the protection of argon to ensure that the NiMoO4Conversion of precursor into NiMoO4Obtaining NiCo2O4@NiMoO4A core-shell structure; preferably, in the step 32), the heat treatment temperature is 400-450 ℃, and the heat treatment time is 1-2 hours.
Preferably, NiCo obtained in said step 3)2O4@NiMoO4In the core-shell structure, the NiCo2O4Is of nanowire structure, the NiMoO4The morphology of (A) is a nanosheet structure.
In another aspect, embodiments of the present invention provide a NiCo2O4@NiMoO4A core-shell structure, wherein said NiCo2O4@NiMoO4The core-shell structure comprises a current collector and NiCo growing on the surface of the current collector2O4And grown on NiCo2O4Surface NiMoO4(ii) a Preferably, the NiMoO4The thickness of the shell layer is preferably 10-20 nm;
preferably, NiCo2O4Is of nanowire structure, the NiMoO4The morphology of (A) is a nanosheet structure.
Preferably, said NiCo2O4@NiMoO4The core-shell structure of NiCo of any one of the above2O4@NiMoO4The core-shell structure is prepared by a preparation method.
Preferably, said NiCo2O4@NiMoO4The core-shell structure is used as an electrode material.
Preferably, said NiCo2O4@NiMoO4The core-shell structure is used as an electrode material of a supercapacitor.
Compared with the prior art, the NiCo of the invention2O4@NiMoO4The core-shell structure and the preparation method thereof have at least the following beneficial effects:
1. NiCo of the embodiment of the invention2O4@NiMoO4The core-shell structure and the preparation method thereof regulate and control NiMoO by a simple method of controlling the concentration of urea in the hydrothermal reaction for preparing a shell layer4The thickness of the shell layer is used for optimizing the electrochemical performance of the core-shell structure. The simple regulation and control method is provided for the first time by the invention. The invention provides a method for preparing a high-performance supercapacitor electrode material, which is simple and easy to implement.
2. NiCo of the embodiment of the invention2O4@NiMoO4In the core-shell structure and the preparation method thereof, the concentration of urea is controlled to be 0.25-0.4mol/L in the hydrothermal reaction for preparing the shell layer to obtain NiCo2O4@NiMoO4The core-shell structure has the best electrochemical performance.
3. NiCo of the embodiment of the invention2O4@NiMoO4The core-shell structure and the preparation method thereof do not use organic solvent, and water is used as the only solvent, so that the pollution to the environment is small; the equipment is simple, the main preparation equipment is an oven and a tube furnace, and the cost is low; the method for regulating and controlling the thickness of the shell layer by changing the concentration of urea is simple and has strong operability; the obtained core-shell structure directly grows on the current collector and can be used as a self-supporting electrode material without a complicated electrode preparation process; NiCo with optimum shell thickness2O4@NiMoO4The core-shell structure shows the highest specific capacitance as an electrode material.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a NiCo sample prepared according to an embodiment of the present invention2O4Carbon cloth and NiCo2O4@NiMoO4An X-ray photoelectron energy spectrum of a core-shell structure; wherein the curve a is NiCo2O4X-ray photoelectron spectrum of carbon cloth with NiCo curve b2O4@NiMoO4X-ray of core-shell structureLine photoelectron energy spectrogram.
FIG. 2 is a NiCo sample prepared according to an embodiment of the present invention2O4Carbon cloth and NiCo2O4@NiMoO4Scanning electron microscope pictures of core-shell structures; wherein, a is NiCo2O4Scanning electron microscope pictures of the carbon cloth; b is the first NiCo2O4@NiMoO4Scanning electron microscope pictures of core-shell structures; c is the second NiCo2O4@NiMoO4Scanning electron microscope pictures of core-shell structures; d is the third NiCo2O4@NiMoO4Scanning electron microscope pictures of core-shell structures.
FIG. 3 is a NiCo sample prepared according to an embodiment of the present invention2O4Carbon cloth and NiCo2O4@NiMoO4Core-shell structure at 20mV s-1Cyclic voltammogram of time; wherein the curve a is NiCo2O4Carbon cloth at 20mV s-1Cyclic voltammogram of time; curve b is the first NiCo2O4@NiMoO4Core-shell structure at 20mV s-1Cyclic voltammogram of time; curve c is second NiCo2O4@NiMoO4Core-shell structure at 20mV s-1Cyclic voltammogram of time; third NiCo of d-Curve2O4@NiMoO4Core-shell structure at 20mV s-1Cyclic voltammogram of time.
FIG. 4 is a NiCo sample prepared according to an embodiment of the present invention2O4Carbon cloth and NiCo2O4@NiMoO4The core-shell structure is 2mA cm-2Constant current charge and discharge curve diagram. Wherein the curve a is NiCo2O4Carbon cloth at 2mA cm-2A time constant current charge-discharge curve diagram; curve b is the first NiCo2O4@NiMoO4The core-shell structure is 2mA cm-2A time constant current charge-discharge curve diagram; c curve second NiCo2O4@NiMoO4The core-shell structure is 2mA cm-2A time constant current charge-discharge curve diagram; curve d is third NiCo2O4@NiMoO4The core-shell structure is 2mA cm-2Constant timeAnd (4) current charging and discharging curve diagrams.
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the predetermined object, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
In one aspect, embodiments of the present invention provide a NiCo2O4@NiMoO4The preparation method of the core-shell structure comprises the following steps:
step 1): growing NiCo on a current collector2O4After the precursor is nanostructured, NiCo on the current collector is put2O4Conversion of precursors to NiCo2O4Obtaining NiCo2O4Current collector.
Specifically, the step 1) includes the steps of:
step 11): transferring the current collector and the hydrothermal reaction solution into a hydrothermal reaction device for hydrothermal reaction, and growing NiCo on the current collector2O4Precursor nanowire structure to obtain NiCo2O4Precursor/current collector.
Preferably, step 11) is specifically: preparing Ni (NO)3)2、Co(NO3)2Uniformly stirring the mixed solution of urea and the mixed solution, transferring the mixed solution into a high-pressure reaction kettle, vertically putting clean carbon cloth (the current collector adopts the carbon cloth), and growing NiCo on the carbon cloth by adopting a hydrothermal reaction2O4And (3) precursor nano structure. Wherein said Ni (NO)3)20.5 to 2mmol of Co (NO)3)2The mole number of the urea is 1-4 mmol, the concentration of the urea is 0.25-0.6 mol/L, and the volume of the deionized water is 10-40 mL. Wherein the hydrothermal reaction temperature in the step 11) is 120-160 ℃, and the hydrothermal reaction time is 4-10 hours.
Step 12): for the NiCo2O4And cleaning and drying the precursor/current collector.
Preferably, step 12) is specifically: NiCo with deionized water and ethanol2O4Sequentially carrying out ultrasonic cleaning on the precursor/current collector for multiple times, and then cleaning the cleaned NiCo2O4And putting the precursor/current collector into an oven for drying and carrying out drying treatment. Wherein the drying temperature is 60-80 ℃, and the drying time is 12-24 hours.
Step 13): for the NiCo2O4Heat treating the precursor/current collector to obtain NiCo2O4Conversion of precursors to NiCo2O4Obtaining NiCo2O4Current collector.
In this step, the nanowire structure is maintained, NiCo2O4NiCo in current collector2O4Is a nanowire.
Preferably, the step 13) is specifically: mixing NiCo2O4Precursor/current collector (grown with NiCo)2O4Carbon cloth of precursor) is put into a tube furnace and heat treatment is carried out under the protection of argon, NiCo2O4Conversion of the precursor to NiCo2O4。
In the step 13), the heat treatment temperature is 300-400 ℃, and the heat treatment time is 1-2 hours.
Step 2): mixing the hydrothermal reaction solution and NiCo2O4Putting the current collector into a hydrothermal reaction device for hydrothermal reaction, and putting the NiCo into the reactor for hydrothermal reaction2O4NiCo in Current collector2O4A layer of NiMoO grows on the surface4Precursor nanosheet structure to obtain NiCo2O4@NiMoO4And (3) a precursor core-shell structure.
The concentration of urea in the hydrothermal reaction solution in the step 2) is 0.1-0.75 mol/L; preferably, the concentration of urea in the hydrothermal reaction solution in the step 2) is 0.25-0.4 mol/L.
Preferably, the hydrothermal reaction solution in the step 2) is selected from the group consisting of nickel salt and solute,A mixed solution of molybdate and urea; preferably, the nickel salt is Ni (NO)3)2The molybdate is Na2MoO4(ii) a Preferably, in the hydrothermal reaction solution of step 2), the molar number of the nickel salt is 0.36 to 0.72mmol, the molar number of the molybdate is 0.36 to 0.72mmol, and the volume of water is 20 to 40 mL.
Preferably, step 2) is specifically: preparing hydrothermal reaction solution, stirring uniformly, transferring into high-pressure reaction kettle, and growing NiCo2O4The carbon cloth is vertically put into a reaction kettle for hydrothermal reaction, and is put into NiCo2O4A layer of NiMoO grows on the surface4And (3) precursor nano structure.
Preferably, the temperature of the hydrothermal reaction is controlled to be 120-160 ℃, and the time of the hydrothermal reaction is controlled to be 4-8 hours.
In the step, the concentration of urea in the hydrothermal reaction solution of the step 2) is controlled to obtain the set NiMoO4NiCo with shell thickness2O4@NiMoO4A core-shell structure. Specifically, when the concentration of urea in the hydrothermal reaction solution in the step 2) is more than or equal to 0.1mol/L and less than 0.25mol/L, the first NiCo obtained in the step 3) is2O4@NiMoO4A core-shell structure. When the concentration of urea in the hydrothermal reaction solution in the step 2) is 0.25-0.4mol/L, obtaining a second NiCo in the step 3)2O4@NiMoO4A core-shell structure. When the concentration of urea in the hydrothermal reaction solution in the step 2) is more than 0.4mol/L and less than or equal to 0.75mol/L, the third NiCo obtained in the step 3)2O4@NiMoO4A core-shell structure. Wherein the first NiCo2O4@NiMoO4The thickness of the shell layer of the core-shell structure is larger than that of the second NiCo2O4@NiMoO4The thickness of the shell layer of the core-shell structure is more than that of the third NiCo2O4@NiMoO44 shell layer thickness of core-shell structure. The second NiCo2O4@NiMoO4Specific capacitance of core-shell structure is larger than third NiCo2O4@NiMoO4Specific capacitance of core-shell structure is greater than first NiCo2O4@NiMoO4Specific electricity of core-shell structureAnd (4) carrying out the following steps.
Step 3): mixing NiCo2O4@NiMoO4NiMoO in precursor core-shell structure4Conversion of precursor into NiMoO4Obtaining NiCo2O4@NiMoO4A core-shell structure.
In the process of the step 3), the morphology of the nanosheet of the shell layer is maintained.
Specifically, the step 3) includes:
step 31): for the NiCo2O4@NiMoO4And cleaning and drying the precursor core-shell structure.
Preferably, step 31) is specifically: sequentially reacting the NiCo with water and ethanol2O4@NiMoO4After the precursor core-shell structure is subjected to ultrasonic cleaning for multiple times, the NiCo is subjected to ultrasonic cleaning2O4@NiMoO4Putting the precursor core-shell structure into an oven for drying; preferably, in the step 31), the temperature of the drying treatment is 60-80 ℃, and the time of the drying treatment is 12-24 hours.
Step 32): for the NiCo2O4@NiMoO4Heat treating the precursor core-shell structure to obtain NiMoO4Conversion of precursor into NiMoO4Obtaining NiCo2O4@NiMoO4A core-shell structure.
Preferably, in step 32), NiCo will be grown2O4@NiMoO4Putting the current collector with the precursor core-shell structure into a tube furnace, and carrying out heat treatment under the protection of argon to ensure that the NiMoO4Conversion of precursor into NiMoO4Obtaining NiCo2O4@NiMoO4A core-shell structure; preferably, in the step 32), the heat treatment temperature is 400-450 ℃, and the heat treatment time is 1-2 hours.
In another aspect, the invention also provides a NiCo2O4@NiMoO4A core-shell structure, wherein said NiCo2O4@NiMoO4The core-shell structure of NiCo of any one of the above2O4@NiMoO4Preparation method of core-shell structureIs prepared. In the NiCo prepared2O4@NiMoO4In the core-shell structure, the core layer NiCo2O4Is in the shape of a nanowire structure and the shell layer NiMoO4The morphology of (A) is a nanosheet structure. Preferably, said NiCo2O4@NiMoO4The core-shell structure is used as an electrode material; preferably, said NiCo2O4@NiMoO4The core-shell structure is used as an electrode material of a supercapacitor.
The present invention will be further illustrated by the following specific experimental examples.
Example 1
Step 1) a hydrothermal reaction solution (the hydrothermal reaction solution comprises the following components: 0.5mmol Ni (NO)3)2+1mmol Co(NO3)2+2.5mmol urea +10mL deionized water) was poured into the autoclave and the carbon cloth was immersed in the hydrothermal reaction solution. Sealing the reaction kettle, and then placing the reaction kettle in an oven for hydrothermal reaction at the temperature of 160 ℃ for 4 hours to obtain the nano-wire NiCo growing on the surface of the carbon cloth2O4Precursor (i.e., NiCo)2O4Precursor/carbon cloth). By using deionized water and ethanol on NiCo2O4And cleaning the precursor/carbon cloth for 3 times, and drying in an oven at 60 ℃ for 24 hours. Drying the NiCo2O4Putting the precursor/carbon cloth into a tube furnace, and carrying out heat treatment under the protection of argon, wherein the heat treatment temperature is 300 ℃, and the heat treatment time is 2 hours, so that the nano linear NiCo2O4Transformation of precursor into nanowire-like NiCo2O4Obtaining NiCo2O4A carbon cloth.
Step 2) a hydrothermal reaction solution (the hydrothermal reaction solution comprises the following components: 0.36mmol Ni (NO)3)2+0.36mmolNa2MoO4+7.5mmol urea +20mL deionized water; the concentration of urea is 0.375mol/L) is poured into a reaction kettle; then adding NiCo2O4The/carbon cloth is vertically immersed in the hydrothermal reaction solution. Sealing the reaction kettle, and then placing the reaction kettle in an oven for hydrothermal reaction at the temperature ofThe hydrothermal reaction is carried out for 4 hours at the temperature of 120 ℃, and NiCo growing on the surface of the carbon cloth is obtained2O4@NiMoO4And (3) a precursor core-shell structure. Here, the morphology of the NiMoO4 precursor is nano-flake.
Step 3) adding deionized water and ethanol to NiCo2O4@NiMoO4Cleaning the precursor core-shell structure for 3 times, and drying in an oven; wherein the drying treatment is carried out at 80 deg.C for 12 hr. Drying the NiCo2O4@NiMoO4Placing the precursor core-shell structure in a tube furnace, carrying out heat treatment under the protection of argon, wherein the heat treatment temperature is 430 ℃, the heat treatment time is 1.5 hours, and adding NiMoO4Conversion of precursor into NiMoO4，NiCo2O4The phase is not changed to obtain a second NiCo2O4@NiMoO4A core-shell structure. Wherein the second NiCo2O4@NiMoO4In the core-shell structure, the core layer NiCo2O4The shape of the nano-wire is a nanowire structure and a shell NiMoO4Is of a nano-sheet structure
Electrochemical performance was tested using three electrodes. 6M KOH as electrolyte, platinum sheet as auxiliary electrode, mercury/mercury oxide as reference electrode, and NiCo2O4Carbon cloth, NiCo2O4@NiMoO4The core-shell structure is used as a working electrode.
Example 2
Step 1) a hydrothermal reaction solution (the hydrothermal reaction solution comprises the following components: 1mmol Ni (NO)3)2+2 mmol Co(NO3)2+10mmol urea +20mL deionized water) was poured into the autoclave and a carbon cloth was immersed in the hydrothermal reaction solution. Sealing the reaction kettle, and then placing the reaction kettle in an oven for hydrothermal reaction at the temperature of 140 ℃ for 8 hours to obtain the nanowire NiCo growing on the surface of the carbon cloth2O4Precursor (i.e., NiCo)2O4Precursor/carbon cloth). By using deionized water and ethanol on NiCo2O4Cleaning the precursor/carbon cloth for 3 times, and drying in an oven at 80 deg.C for 12 hr. Drying the NiCo2O4Putting the precursor/carbon cloth into a tube furnace, and carrying out heat treatment under the protection of argon, wherein the heat treatment temperature is 400 ℃, and the heat treatment time is 1 hour, so that the nano linear NiCo2O4Transformation of precursor into nanowire-like NiCo2O4Obtaining NiCo2O4A carbon cloth.
Step 2) a hydrothermal reaction solution (the hydrothermal reaction solution comprises the following components: 0.72mmol Ni (NO)3)2+0.72mmolNa2MoO4+30mmol urea +40mL deionized water; the concentration of urea is 0.75mol/L) is poured into a reaction kettle; then adding NiCo2O4The/carbon cloth is vertically immersed in the hydrothermal reaction solution. Sealing the reaction kettle, and then placing the reaction kettle in a drying oven for hydrothermal reaction at 120 ℃ for 4 hours to obtain NiCo growing on the surface of the carbon cloth2O4@NiMoO4And (3) a precursor core-shell structure. Here, NiMoO4The shape of the precursor is nano-flake.
Step 3) adding deionized water and ethanol to NiCo2O4@NiMoO4Cleaning the precursor core-shell structure for 3 times, and drying in an oven; wherein the drying treatment temperature is 70 deg.C and the drying treatment time is 20 hr. Drying the NiCo2O4@NiMoO4Placing the precursor core-shell structure in a tube furnace, carrying out heat treatment under the protection of argon, wherein the heat treatment temperature is 400 ℃, the heat treatment time is 2 hours, and adding NiMoO4Conversion of precursor into NiMoO4，NiCo2O4The phase is not changed to obtain a third NiCo2O4@NiMoO4A core-shell structure. Wherein the third NiCo2O4@NiMoO4In the core-shell structure, the core layer NiCo2O4The shape of the nano-wire is a nanowire structure and a shell NiMoO4Is of a nano-sheet structure
Electrochemical performance was tested using three electrodes. 6M KOH as electrolyte, platinum sheet as auxiliary electrode, mercury/mercury oxide as reference electrode, and NiCo2O4Carbon cloth, NiCo2O4@NiMoO4Core-shell structureAs the working electrode.
Example 3
Step 1) a hydrothermal reaction solution (the hydrothermal reaction solution comprises the following components: 2mmol Ni (NO)3)2+4 mmol Co(NO3)2+24mmol urea +40mL deionized water) was poured into the autoclave and a carbon cloth was immersed in the hydrothermal reaction solution. Sealing the reaction kettle, and then placing the reaction kettle in an oven for hydrothermal reaction at the temperature of 120 ℃ for 10 hours to obtain the nano-wire NiCo growing on the surface of the carbon cloth2O4Precursor (i.e., NiCo)2O4Precursor/carbon cloth). By using deionized water and ethanol on NiCo2O4And cleaning the precursor/carbon cloth for 3 times, and drying in an oven at 70 ℃ for 20 hours. Drying the NiCo2O4Putting the precursor/carbon cloth into a tube furnace, and carrying out heat treatment under the protection of argon, wherein the heat treatment temperature is 350 ℃, and the heat treatment time is 1.5 hours, so that the nanowire NiCo2O4Transformation of precursor into nanowire-like NiCo2O4Obtaining NiCo2O4A carbon cloth.
Step 2) a hydrothermal reaction solution (the hydrothermal reaction solution comprises the following components: 0.54mmol Ni (NO)3)2+0.54mmolNa2MoO4+3mmol urea +30mL deionized water; the concentration of urea is 0.1mol/L) is poured into a reaction kettle; then adding NiCo2O4The/carbon cloth is vertically immersed in the hydrothermal reaction solution. Sealing the reaction kettle, and then placing the reaction kettle in a drying oven for hydrothermal reaction at 120 ℃ for 4 hours to obtain NiCo growing on the surface of the carbon cloth2O4@NiMoO4And (3) a precursor core-shell structure. Here, NiMoO4The shape of the precursor is nano-flake.
Step 3) adding deionized water and ethanol to NiCo2O4@NiMoO4Cleaning the precursor core-shell structure for 3 times, and drying in an oven; wherein the drying treatment temperature is 60 deg.C and the drying treatment time is 24 hr. Drying the NiCo2O4@NiMoO4Precursor bodyPlacing the core-shell structure in a tube furnace, carrying out heat treatment under the protection of argon, wherein the heat treatment temperature is 450 ℃, the heat treatment time is 1 hour, and adding NiMoO4Conversion of precursor into NiMoO4，NiCo2O4The phase is not changed to obtain the first NiCo2O4@NiMoO4A core-shell structure. Wherein the first NiCo2O4@NiMoO4In the core-shell structure, the core layer NiCo2O4The shape of the nano-wire is a nanowire structure and a shell NiMoO4Is of a nano-sheet structure
Electrochemical performance was tested using three electrodes. 6M KOH as electrolyte, platinum sheet as auxiliary electrode, mercury/mercury oxide as reference electrode, and NiCo2O4Carbon cloth, NiCo2O4@NiMoO4The core-shell structure is used as a working electrode.
NiCo prepared by the above examples2O4Carbon cloth, first NiCo2O4@NiMoO4Core-shell structure (concentration of urea in hydrothermal reaction solution prepared in example 3 and step 2 is 0.1mol/L), second NiCo2O4@NiMoO4Core-shell structure (concentration of urea in hydrothermal reaction solution prepared in example 1 and step 2 is 0.25-0.4mol/L), and third NiCo2O4@NiMoO4Core-shell structure (prepared in example 2, concentration of urea in hydrothermal reaction solution in step 2 is 0.75mol/L) was subjected to test structural analysis as follows:
1. in the first hydrothermal reaction (step 1), the concentration of urea is changed for NiCo2O4The shape of the nanowire is not greatly influenced. However, in the second hydrothermal reaction (step 2), NiMoO with different shell thicknesses can be obtained by changing the urea concentration4Nanosheets.
2. As can be seen from fig. 1: with NiCo2O4Carbon to carbon ratio, NiCo2O4@NiMoO4Presence of Mo in core-shell structure6+The peak position of the combination of Ni and Co demonstrates the formation of NiCo2O4And NiMoO4。
3. As can be seen from fig. 2: when it is two timesWhen the concentration of urea in the hydrothermal reaction solution (the hydrothermal reaction solution in step 2) is 0.1mol/L, thicker NiMoO is obtained4Nanosheets; when the concentration of the urea is 0.25-0.4mol/L, obtaining thinner NiMoO4Nanosheets; when the concentration of urea is 0.75mol/L, thinner NiMoO is obtained4Nanosheets. I.e. the first NiCo2O4@NiMoO4The thickness of the shell layer of the core-shell structure is larger than that of the second NiCo2O4@NiMoO4The thickness of the shell layer of the core-shell structure is more than that of the third NiCo2O4@NiMoO4Shell thickness of core-shell structure.
4. As can be seen from fig. 3: area enclosed by cyclic voltammogram: NiCo with thinner shell2O4@NiMoO4Shell NiCo with core-shell structure2O4@NiMoO4Core-shell structure, more than thick shell layer NiCo2O4@NiMoO4Core-shell structure & gt NiCo2O4Carbon cloth, which shows that NiCo with a thinner shell layer thickness is obtained when the concentration of urea is 0.25-0.4mol/L2O4@NiMoO4The specific capacitance of the electrode with the core-shell structure is highest. I.e. the second NiCo2O4@NiMoO4Specific capacitance of core-shell structure is larger than third NiCo2O4@NiMoO4Specific capacitance of core-shell structure is greater than first NiCo2O4@NiMoO4Specific capacitance of core-shell structure.
5. As can be seen from fig. 4, the discharge time: relatively thin shell NiCo2O4@NiMoO4Shell NiCo with core-shell structure2O4@NiMoO4Core-shell structure, more than thick shell layer NiCo2O4@NiMoO4Core-shell structure & gt NiCo2O4Carbon cloth, also indicating that NiCo with a thinner shell thickness is obtained when the urea concentration is 0.25-0.4mol/L2O4@NiMoO4The core-shell structure has the highest specific capacitance. I.e. the second NiCo2O4@NiMoO4Specific capacitance of core-shell structure is larger than third NiCo2O4@NiMoO4Specific capacitance of core-shell structure is greater than first NiCo2O4@NiMoO4Specific capacitance of core-shell structure.
In addition, as can be seen from a scanning electron microscope, the thicknesses of the nanosheets of the three products obtained by regulating and controlling the concentration of urea are obviously different. A first NiCo2O4@NiMoO4The thickness of a shell layer in the core-shell structure is about 20-50nm, and the size of the nano-sheet is about 100 nm. A second NiCo2O4@NiMoO4The thickness of the shell layer in the core-shell structure is about 10 nanometers, the size of the nanosheet is gradually increased from the top end to the tail end, and the size of the tail end nanosheet can reach about 150 nanometers. Third NiCo2O4@NiMoO4The thickness of the shell layer of the core-shell structure is difficult to be seen by a scanning electron microscope, the thickness is in a nanometer level by visual inspection, and the size of the nanosheet is about 10 nanometers. The contrast between the nanosheets (shells) and nanowires (cores) is sharp as seen by the inset in the d picture in fig. 2, indicating a very thin shell thickness.
In summary, NiCo of the embodiments of the present invention2O4@NiMoO4The core-shell structure and the preparation method thereof regulate and control NiMoO by a simple method of controlling the concentration of urea in the hydrothermal reaction for preparing a shell layer4The thickness of the shell layer is used for optimizing the electrochemical performance of the core-shell structure. The simple regulation and control method is provided for the first time by the invention. The invention provides a method for preparing a high-performance supercapacitor electrode material, which is simple and easy to implement.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (14)
1. NiCo2O4@NiMoO4The preparation method of the core-shell structure is characterized by comprising the following steps:
step 1): growing NiCo on a current collector2O4After the precursor, NiCo on the current collector is added2O4Conversion of precursors to NiCo2O4Obtaining NiCo2O4A current collector;
step 2): mixing the hydrothermal reaction solution and NiCo2O4Putting the current collector into a hydrothermal reaction device for hydrothermal reaction, and putting the NiCo into the reactor for hydrothermal reaction2O4NiCo in Current collector2O4Overgrowth of NiMoO4Precursor to obtain NiCo2O4@NiMoO4A precursor core-shell structure;
step 3): mixing NiCo2O4@NiMoO4NiMoO in precursor core-shell structure4Conversion of precursor into NiMoO4Obtaining NiCo2O4@NiMoO4A core-shell structure;
wherein the concentration of urea in the hydrothermal reaction solution of the step 2) is controlled to obtain the set NiMoO4NiCo with shell thickness2O4@NiMoO4A core-shell structure;
the concentration of urea in the hydrothermal reaction solution in the step 2) is 0.1-0.75 mol/L;
wherein, when the concentration of urea in the hydrothermal reaction solution in the step 2) is more than or equal to 0.1mol/L and less than 0.25mol/L, the first NiCo obtained in the step 3) is2O4@NiMoO4A core-shell structure;
when the concentration of urea in the hydrothermal reaction solution in the step 2) is 0.25-0.4mol/L, obtaining a second NiCo in the step 3)2O4@NiMoO4A core-shell structure;
when the concentration of urea in the hydrothermal reaction solution in the step 2) is more than 0.4mol/L and less than or equal to 0.75mol/L, the third NiCo obtained in the step 3)2O4@NiMoO4A core-shell structure;
wherein the first NiCo2O4@NiMoO4The thickness of the shell layer of the core-shell structure is larger than that of the second NiCo2O4@NiMoO4The thickness of the shell layer of the core-shell structure is more than that of the third NiCo2O4@NiMoO4Shell thickness of core-shell structure.
2. The NiCo of claim 12O4@NiMoO4The preparation method of the core-shell structure is characterized in thatSaid second NiCo2O4@NiMoO4Specific capacitance of core-shell structure is larger than third NiCo2O4@NiMoO4Specific capacitance of core-shell structure is greater than first NiCo2O4@NiMoO4Specific capacitance of core-shell structure.
3. The NiCo of claim 1 or 22O4@NiMoO4The preparation method of the core-shell structure is characterized in that the hydrothermal reaction solution in the step 2) is a mixed solution of nickel salt, molybdate and urea as a solute.
4. The NiCo of claim 32O4@NiMoO4The preparation method of the core-shell structure is characterized in that in the hydrothermal reaction solution in the step 2), the mole number of nickel salt is 0.36-0.72 mmol, the mole number of molybdate is 0.36-0.72 mmol, and the volume of water is 20-40 mL.
5. The NiCo of claim 42O4@NiMoO4The preparation method of the core-shell structure is characterized in that the nickel salt is Ni (NO)3)2The molybdate is Na2MoO4。
6. The NiCo of claim 1 or 22O4@NiMoO4The preparation method of the core-shell structure is characterized in that in the step 2), the temperature of the hydrothermal reaction is controlled to be 120-160 ℃, and the time of the hydrothermal reaction is controlled to be 4-8 hours; and/or
The hydrothermal reaction device is a high-pressure reaction kettle.
7. The NiCo of claim 12O4@NiMoO4The preparation method of the core-shell structure is characterized in that the step 1) comprises the following steps:
step 11): transferring the current collector and the hydrothermal reaction solution into a hydrothermal reaction device for hydrothermal reaction, and growing NiCo on the current collector2O4Precursor nano structure to obtain NiCo2O4A precursor/current collector;
step 12): for the NiCo2O4Cleaning and drying the precursor/current collector;
step 13): for the NiCo2O4Heat treating the precursor/current collector to obtain NiCo2O4Conversion of precursors to NiCo2O4Obtaining NiCo2O4Current collector.
8. The NiCo of claim 72O4@NiMoO4The preparation method of the core-shell structure is characterized in that the current collector adopts carbon cloth; and/or
The hydrothermal reaction device in the step 11) is a high-pressure reaction kettle; and/or
In the step 11), the temperature of the hydrothermal reaction is 120-160 ℃, and the time of the hydrothermal reaction is 4-10 hours.
9. The NiCo of claim 72O4@NiMoO4The preparation method of the core-shell structure is characterized in that the hydrothermal reaction solution in the step 11) is a mixed solution of nickel salt, cobalt salt and urea as solutes.
10. The NiCo of claim 92O4@NiMoO4The preparation method of the core-shell structure is characterized in that,
in the step 11), Ni (NO) is selected as the nickel salt in the hydrothermal reaction solution3)2Co (NO) is selected as cobalt salt3)2(ii) a And/or
The concentration of urea in the hydrothermal reaction solution in the step 11) is 0.25-0.6 mol/L; and/or
In the hydrothermal reaction solution in the step 11), the mole number of nickel salt is 0.5-2 mmol, the mole number of cobalt salt is 1-4 mmol, and the volume of deionized water is 10-40 mL.
11. The NiCo of claim 72O4@NiMoO4The preparation method of the core-shell structure is characterized in that the step 12) is specifically as follows: sequential treatment of NiCo with Water and ethanol2O4After the precursor/current collector is subjected to ultrasonic cleaning for multiple times, NiCo is added2O4Putting the precursor/current collector into an oven for drying treatment; wherein the temperature of the drying treatment is 60-80 ℃, and the time of the drying treatment is 12-24 hours; and/or
The step 13) is specifically as follows: mixing the NiCo2O4Putting the precursor/current collector into a tube furnace, carrying out heat treatment under the protection of argon, and adding NiCo2O4Conversion of precursors to NiCo2O4Obtaining NiCo2O4A current collector; wherein the heat treatment temperature is 300-400 ℃, and the heat treatment time is 1-2 hours.
12. The NiCo of claim 12O4@NiMoO4The preparation method of the core-shell structure is characterized in that the step 3) comprises the following steps:
step 31): for the NiCo2O4@NiMoO4Cleaning and drying the precursor core-shell structure;
step 32): for the NiCo2O4@NiMoO4Heat treating the precursor core-shell structure to obtain NiMoO4Conversion of precursor into NiMoO4Obtaining NiCo2O4@NiMoO4A core-shell structure.
13. The NiCo of claim 122O4@NiMoO4The preparation method of the core-shell structure is characterized in that,
in the step 31), water and ethanol are adopted to sequentially react the NiCo2O4@NiMoO4After the precursor core-shell structure is subjected to ultrasonic cleaning for multiple times, the NiCo is subjected to ultrasonic cleaning2O4@NiMoO4Putting the precursor core-shell structure into an oven for drying; wherein in the step 31)The drying temperature is 60-80 ℃, and the drying time is 12-24 hours; and/or
In the step 32), NiCo is grown2O4@NiMoO4Putting the current collector with the precursor core-shell structure into a tube furnace, and carrying out heat treatment under the protection of argon to ensure that the NiMoO4Conversion of precursor into NiMoO4Obtaining NiCo2O4@NiMoO4A core-shell structure; in the step 32), the heat treatment temperature is 400-450 ℃, and the heat treatment time is 1-2 hours.
14. The NiCo of any of claims 1-2, 4-5, 7-132O4@NiMoO4The preparation method of the core-shell structure is characterized in that NiCo obtained in the step 3)2O4@NiMoO4In the core-shell structure, NiCo2O4The shape of the nuclear layer is a nanowire structure, NiMoO4The shape of the shell layer is a nano-sheet structure.
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| 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 |
|---|
| Hierarchical core-shell NiCo2O4@NiMoO4 nanowires grown on carbon cloth as integrated electrode for high-performance supercapacitors;Liang Huang等;《nature》;20160812;第1-8页 * |
| Urea-Assisted Room Temperature Stabilized Metastable β‑NiMoO4: Experimental and Theoretical Insights into its Unique Bifunctional Activity toward Oxygen Evolution and Supercapacitor;Satyajit Ratha等;《ACS Applied Materials & Interfaces》;20170401;第9640？9653页 * |
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