CN108806995B - A kind of g-C3N4@NiCo2O4The preparation method of core-shell structure - Google Patents
A kind of g-C3N4@NiCo2O4The preparation method of core-shell structure Download PDFInfo
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- CN108806995B CN108806995B CN201810587941.8A CN201810587941A CN108806995B CN 108806995 B CN108806995 B CN 108806995B CN 201810587941 A CN201810587941 A CN 201810587941A CN 108806995 B CN108806995 B CN 108806995B
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910005949 NiCo2O4 Inorganic materials 0.000 claims abstract description 83
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 47
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004202 carbamide Substances 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- 239000006260 foam Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 9
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims abstract description 7
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910003266 NiCo Inorganic materials 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 15
- 229960004756 ethanol Drugs 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 229940125717 barbiturate Drugs 0.000 description 44
- 239000002131 composite material Substances 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000003990 capacitor Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000007812 deficiency Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of g-C3N4@NiCo2O4The preparation method of core-shell structure includes the following steps: that nickel foam is ultrasonically treated by (1) in hydrochloric acid solution, cleans and be dried in vacuo, and weighs Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and urea dissolution solution respectively in the mixed liquor of alcohol water；(2) processed nickel foam and mixed liquor are transferred in reaction kettle simultaneously and react 8, natural cooling, washing is dried to obtain NiCo2O4Presoma；(3) BA ethanol solution is configured, by NiCo2O4Presoma impregnates wherein, obtains BA@NiCo2O4Presoma；(4) urea liquid is configured, and by BA@NiCo2O4Presoma impregnates in urea liquid, dry, obtains urea@BA@NiCo2O4Presoma；(5) by urea@BA@NiCo2O4Presoma is calcined to obtain g-C3N4@NiCo2O4Core-shell structure.
Description
Technical field
The invention belongs to inorganic functional material technical field more particularly to a kind of g-C3N4@NiCo2O4The system of core-shell structure
Preparation Method.
Background technique
With the fast development of global economy, traditional fossil energy is sharply consumed, and energy problem becomes 21st century hardly possible
One of topic.Therefore more efficient, cleaning, sustainable energy are developed to people and is proposed with energy conversion and the new technology of storage
Urgent demand.Recently as various energy technologys, the rise of the reproducible new energy technology of cleaning, as electric car, with
And secondary energy sources utilize etc., finding suitable energy storage device is wherein vital link.Electrochemical capacitor is one
A kind of novel energy storage apparatus of the kind between traditional capacitor and rechargeable battery, it is because of its high power density, long use
Service life and its filled up blank between traditional capacitor (playing the role of high power density) and battery (high energy density)
And increasingly attract the attention of people.Compared with traditional capacitor, supercapacitor has biggish storage capacity, stores energy
Power can reach 20-200 times of traditional capacitor.And compared with battery, especially compared with lithium ion battery etc., supercapacitor
With higher power density and cyclical stability.In addition, supercapacitor also have charge/discharge speed it is fast, it is high-efficient, to ring
Border is pollution-free, has extended cycle life, the features such as use temperature range is wide, highly-safe.Since appearing on the market, the whole world needs supercapacitor
The amount of asking rapid expansion, it has also become new industry bright spot in field of chemical power source.
Nickel foam is a kind of new function material for coming across the end of the eighties in last century, and metallic nickel is mainly carried out deep processing
Manufactured porous, expanded metal, with the porous skeleton structure of its high porosity, high-specific surface area and high conductivity and low electricity
Resistance, characteristic that is inexpensive, corrosion-resistant and being easy to amplify rapidly become research hotspot.The three dimensional skeletal structure of nickel foam can be effective
Reduction electrode material agglomeration in the preparation, improve the chemical property of electrode material, and the electric conductivity of nickel foam
Can be excellent, it is a kind of ideal conductive carrier.
g-C3N3It is that a kind of hardness is high, density is low, chemical stability is high, wearability is strong, bio-compatibility is good and preparation is simple
Two-dimensional layered-structure material, have huge development potentiality in terms of using energy source, photocatalysis and pollution.Mesh
Preceding g-C3N4It is mainly used in photocatalysis field, the relevant report in supercapacitor field is less, and g-C3N4It is easy to reunite, it leads
The deficiencies of causing specific capacitance lower and low electric bridge carrier mobility all limits it in supercapacitor field into one
Step development.NiCo2O4Ni is existed simultaneously in material2+/Ni3+And Co2+/Co3+, these ions imparting NiCo2O4The excellent electricity of material
Chemical activity, while NiCo2O4Have many advantages, such as that theoretical specific capacitance is high, preparation process is simple, widely distributed, is a kind of ideal
Electrode material.But single-phase NiCo2O4Crystal structure can generate dilation with charge and discharge, lead to NiCo2O4's
Cycle life is insufficient.
A kind of NiCo is disclosed in patent CN103107025A2O4Preparation method, the patent disclosure it is only single-phase
NiCo2O4Preparation method, not to NiCo2O4Improved, interior resistance is big, the disadvantage of low efficiency and cycle life deficiency still
So exist.A kind of solid grinding method is disclosed in patent CN106971863A prepares a kind of g-C3N4/NiCo2S4Composite material
Method, the uniformity for preparing composite material is small, and the chemical property for preparing electrode differs greatly.
In view of this, the present invention is specifically proposed.
Summary of the invention
Aiming at the problems existing in the prior art, the object of the present invention is to provide a kind of g-C3N4@NiCo2O4Core-shell structure
Preparation method, preparation method is simple, stable electrochemical property, and specific capacitance is high, and internal resistance is low, and controllability is strong, scale easy to accomplish
Metaplasia produce, be not necessarily to special installation and harsh conditions, can be used as a kind of electrode material of supercapacitor, supercapacitor, can
Large-scale application is arrived in rechargeable battery field.
To achieve the goals above, a kind of g-C provided by the invention3N4@NiCo2O4The preparation method of core-shell structure, including
Following steps:
(1) nickel foam is ultrasonically treated 20min in the hydrochloric acid solution of 0.1mol/L, removes the oxide on surface, cleaned
And be dried in vacuo, it is being 1: 2-3: 36 according to molar ratio, is weighing Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and urea respectively,
Solution is dissolved in the mixed liquor of deionized water and dehydrated alcohol, and the reaction density for controlling nickel nitrate is 0.05-0.1mol/L；
(2) processed nickel foam in step (1) and mixed liquor are transferred in reaction kettle simultaneously, 100~130 DEG C of reactions 8
~12h naturally cools to room temperature, and deionized water is washed 3 times, is dried to obtain NiCo2O4Presoma；
(3) it weighs and occupies NiCo obtained by step (2)2O4Presoma mass percent is the BA of 30%-50%, is configured to
The BA ethanol solution of 0.1-0.3mol/L, by NiCo obtained in step (2)2O4Presoma is immersed in BA ethanol solution, is obtained
BA@NiCo2O4Presoma；
(4) it weighs and occupies BA@NiCo obtained by step (3)2O4Presoma mass percent is the urea of 8%-20%, dissolution
In ethanol, being made into concentration is 0.1-0.25mol/L solution, and by BA@NiCo2O4Presoma impregnates in urea liquid, does
It is dry, obtain urea@BA@NiCo2O4Presoma；
(5) step (4) is obtained into urea@BA@NiCo2O4Presoma obtains g-C in 300-325 DEG C of calcining 2-4h3N4@
NiCo2O4Core-shell structure.
Preferably, deionized water in the mixed liquor of deionized water and dehydrated alcohol in the step (1): dehydrated alcohol volume
Than being 1: 0.5-1.5；
Preferably, the molal weight of BA is 5.2-10.4mmol in the step (3)；
Preferably, NiCo in the step (3)2O4Presoma soaking time in BA ethanol solution is 30-60min；
Preferably, BA@NiCo in the step (4)2O4Presoma soaking time in urea liquid is 20-30min；
Preferably, the g-C that the step (5) obtains3N4@NiCo2O4G-C in core-shell structure3N4With NiCo2O4Mass ratio
It is 0.05-0.1: 1.
It is provided by the invention, it has the following beneficial effects:
1. the present invention first passes through acidolysis and obtains pure nickel foam, using nickel foam as matrix, then, it is hydrated with six
Nickel nitrate and cabaltous nitrate hexahydrate prepare NiCo using hydro-thermal method respectively as nickel source and cobalt source2O4Presoma utilizes
NiCo2O4Presoma@nickel foam is matrix, by infusion method in NiCo2O4Presoma surface coats BA, then is existed by self assembly
BA@NiCo2O4Presoma foam nickel surface coats one layer of urea, obtains g-C finally by calcining3N4@NiCo2O4Core-shell structure
Composite material.On the one hand this composite material has the characteristics of nickel foam stable structure, porosity is high, large specific surface area, be
NiCo2O4The growth of nanometer rods provides more growth sites, on the other hand has g-C3N4The characteristics of stable chemical performance, improves
NiCo2O4The disadvantage of cycle performance deficiency.Meanwhile by the cladding of BA, so that NiCo2O4Nanometer rods and g-C3N4Between
In conjunction with the resistance for more closely, reducing nucleocapsid combination interface, ion conduction rate is improved.These advantages make g-C3N4@
NiCo2O4Composite material of core-shell structure has great application value in supercapacitor, rechargeable battery field.
2. the NiCo that the present invention passes through barbiturates (BA) coating decoration2O4Nano wire passes through BA and g-C3N4Presoma
Organic coupled action of (urea) forms g-C3N4@NiCo2O4Core-shell structure.On the one hand, by NiCo2O4Area load one
The g-C of layer high conductivity3N4, materials conductive performance is improved, material specific capacitance is improved；On the other hand, made by BA intermediate
With enhancing NiCo2O4Nano wire and g-C3N4Binding force, improve ion conduction rate, reduce interface resistance, improve specific capacitance,
It is improved simultaneously, and performance is recycled；Further, NiCo2O4Surface coats sheet g-C3N4Increase the specific surface area of material, improves
Specific capacitance.To sum up, g-C3N4@NiCo2O4The chemical property of composite material of core-shell structure is more excellent, and the interior resistance of material is more
It is small, and preparation method is simple, controllability is strong, large-scale production easy to accomplish, is not necessarily to special installation and harsh conditions.Of the invention
Composite material not only specific capacitance with higher, and there is lower internal resistance and good electrochemical stability.
Detailed description of the invention
Fig. 1 is that the SEM of embodiment 1 provided by the invention schemes.
Fig. 2 is the NiCo of embodiment 1 provided by the invention2O4XRD diagram.
Specific embodiment
The present invention will be further described with attached drawing combined with specific embodiments below, to help the contents of the present invention are understood.
Embodiment 1:
It as shown in Figs. 1-2, is a kind of g-C provided by the invention3N4@NiCo2O4The preparation method of core-shell structure, including such as
Lower step:
(1) nickel foam is ultrasonically treated 20min in the hydrochloric acid solution of 0.1mol/L, removes the oxide on surface, cleaned
And be dried in vacuo, it is being 1: 2: 36 according to molar ratio, is weighing Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and urea respectively, it is molten
Solution in deionized water and dehydrated alcohol mixed liquor, control nickel nitrate reaction density be 0.05mol/L, wherein deionized water and
Dehydrated alcohol in the mixed solvent deionized water: dehydrated alcohol volume ratio is 1: 0.5；
(2) processed nickel foam in step (1) and mixed liquor are transferred in reaction kettle simultaneously, 120 DEG C of reaction 12h, from
It is so cooled to room temperature, deionized water is washed 3 times, and NiCo is dried to obtain2O4Presoma；
(3) it weighs and occupies NiCo obtained by step (2)2O4Presoma mass percent is 30% or molal weight is
The BA of 5.2mmol is configured to the BA ethanol solution of 0.1mol/L, by NiCo obtained in step (2)2O4Presoma is immersed in BA
In ethanol solution, 30min is kept the temperature under the conditions of 80 DEG C, obtains BA@NiCo2O4Presoma；
(4) it weighs and occupies BA@NiCo obtained by step (3)2O4The urea that presoma mass percent is 8%, is dissolved in ethyl alcohol
In, being made into concentration is 0.1mol/L solution, by BA@NiCo obtained in step (3)2O4Presoma impregnates in urea liquid
20min, it is dry, obtain urea@BA@NiCo2O4Presoma；
(5) the urea@BA@NiCo for obtaining step (4)2O4Presoma obtains g-C in 325 DEG C of calcining 2.5h3N4@
NiCo2O4Core-shell structure.
Using the content of elemental analysis method test C, N, Ni, Co content are tested using ICP, obtains g-C3N4@NiCo2O4
G-C in core-shell structure3N4With NiCo2O4Mass ratio be 0.05: 1.
XRD spectra test is carried out to gained sample using Rigaku Smart Lab, is gone out in the XRD spectrogram of gained sample
Existing NiCo2O4And g-C3N4Characteristic peak, illustrate that composite material is successfully prepared.
Electrochemical property test is carried out to gained sample using AUTLAB, gained sample CV curve shows charge and discharge electroxidation
Reduction peak, it was demonstrated that sample is a kind of fake capacitance material, illustrates to can be used as electrode material for super capacitor.
The g-C of this example preparation3N4@NiCo2O4Composite material of core-shell structure, when current density is 0.5A/g, g-
C3N4@NiCo2O4The specific capacitance of core-shell structure combination electrode reaches 736F/g, after 1000 circulation experiments, composite material
Specific capacitance is maintained as 636F/g.
Embodiment 2:
Another preferable g-C provided by the invention3N4@NiCo2O4The preparation method of core-shell structure, includes the following steps:
(1) nickel foam is ultrasonically treated 20min in the hydrochloric acid solution of 0.1mol/L, removes the oxide on surface, cleaned
And be dried in vacuo, it is being 1: 2: 36 according to molar ratio, is weighing Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and urea respectively, it is molten
Solution is in deionized water and dehydrated alcohol mixed liquor, and the reaction density for controlling nickel nitrate is 0.075mol/L, wherein deionized water
It is 1: 1 with deionized water in dehydrated alcohol mixed liquor: dehydrated alcohol volume ratio；
(2) processed nickel foam in step (1) and mixed liquor are transferred in reaction kettle simultaneously, 120 DEG C of reaction 12h, from
It is so cooled to room temperature, deionized water is washed 3 times, and NiCo is dried to obtain2O4Presoma.
(3) it weighs and occupies NiCo obtained by step (2)2O4Presoma mass percent is 40% or molal weight is
The BA of 6.9mmol is configured to the BA ethanol solution of 0.2mol/L, by NiCo obtained in step (2)2O4Presoma is immersed in BA
In ethanol solution, 45min is kept the temperature under the conditions of 80 DEG C, obtains BA@NiCo2O4Presoma；
(4) it weighs and occupies BA@NiCo obtained by step (3)2O4The urea that presoma mass percent is 14%, is dissolved in second
In alcohol, being made into concentration is 0.175mol/L solution, by BA@NiCo obtained in step (3)2O4Presoma soaks in urea liquid
25min is steeped, it is dry, obtain urea@BA@NiCo2O4Presoma；
(5) the urea@BA@NiCo for obtaining step (4)2O4Presoma obtains g-C in 325 DEG C of calcining 2.5h3N4@
NiCo2O4Core-shell structure.
Using the content of elemental analysis method test C, N, Ni, Co content, the g-C3N4@obtained are tested using ICP
G-C in NiCo2O4 core-shell structure3N4With NiCo2O4Mass ratio be 0.75: 1.
XRD spectra test is carried out to gained sample using Rigaku Smart Lab, is gone out in the XRD spectrogram of gained sample
Existing NiCo2O4And g-C3N4Characteristic peak, illustrate that composite material is successfully prepared.
Electrochemical property test is carried out to gained sample using AUTLAB, gained sample CV curve shows charge and discharge electroxidation
Reduction peak, it was demonstrated that sample is a kind of fake capacitance material, illustrates to can be used as electrode material for super capacitor.
The g-C of this example preparation3N4@NiCo2O4Composite material of core-shell structure, when current density is 0.SA/g, g-
C3N4@NiCo2O4The specific capacitance of core-shell structure combination electrode reaches 750F/g, after 1000 circulation experiments, combination electrode
Specific capacitance is maintained as 669F/g.
Embodiment 3:
Another preferable g-C provided by the invention3N4@NiCo2O4The preparation method of core-shell structure, includes the following steps:
(1) nickel foam is ultrasonically treated 20min in the hydrochloric acid solution of 0.1mol/L, removes the oxide on surface, cleaned
And be dried in vacuo, it is being 1: 2: 36 according to molar ratio, is weighing Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and urea respectively, it is molten
Solution in deionized water and dehydrated alcohol mixed liquor, control nickel nitrate reaction density be 0.1mol/L, wherein deionized water and
Deionized water in dehydrated alcohol mixed liquor: dehydrated alcohol volume ratio is 1: 1.5；
(2) processed nickel foam in step (1) and mixed liquor are transferred in reaction kettle simultaneously, 120 DEG C of reaction 12h, from
It is so cooled to room temperature, deionized water is washed 3 times, and NiCo is dried to obtain2O4Presoma.
(3) it weighs and occupies NiCo obtained by step (2)2O4Presoma mass percent is 50% or molal weight is
The BA of 10.4mmol is configured to the BA ethanol solution of 0.3mol/L, by NiCo obtained in step (2)2O4Presoma is immersed in BA
In ethanol solution, 60min is kept the temperature under the conditions of 80 DEG C, obtains BA@NiCo2O4Presoma；
(4) it weighs and occupies BA@NiCo obtained by step (3)2O4The urea that presoma mass percent is 20%, is dissolved in second
In alcohol, being made into concentration is 0.25mol/L solution, by BA@NiCo obtained in step (3)2O4Presoma impregnates in urea liquid
30min, it is dry, obtain urea@BA@NiCo2O4Presoma；
(5) the urea@BA@NiCo for obtaining step (4)2O4Presoma obtains g-C in 325 DEG C of calcining 2.5h3N4@
NiCo2O4Core-shell structure.
Using the content of elemental analysis method test C, N, Ni, Co content are tested using ICP, obtains g-C3N4With NiCo2O4
Mass ratio be 0.1: 1.
XRD spectra test is carried out to gained sample using Rigaku Smart Lab, is gone out in the XRD spectrogram of gained sample
Existing NiCo2O4And g-C3N4Characteristic peak, illustrate that composite material is successfully prepared.
Electrochemical property test is carried out to gained sample using AUTLAB, gained sample CV curve shows charge and discharge electroxidation
Reduction peak, it was demonstrated that sample is a kind of fake capacitance material, illustrates to can be used as electrode material for super capacitor.
This example preparation using nickel foam as matrix, g-C3N4@NiCo2O4Composite material of core-shell structure, when in current density
When for 0.5A/g, g-C3N4@NiCo2O4The specific capacitance of core-shell structure combination electrode reaches 723F/g, is passing through 1000 circulation experiments
Afterwards, the specific capacitance of combination electrode is maintained as 656F/g.
The present invention mainly passes through BA as intermediate, so that g-C3N4In NiCo2O4Surface is uniformly adhered to, and will be formed
Using NiCo2O4 as core, and after being coated using BA, the outer surface regrowth g-C3N4 forms a kind of core-shell structure, can be not only
Reduce the agglomeration of g-C3N4, additionally it is possible to be effectively improved the problem of the cycle life deficiency of NiCo2O4, binding force is improved, mentioned
High carrier conduction velocity, further increases capacitor.The g-C of preparation3N4@NiCo2O4Composite material of core-shell structure has electrochemistry
Performance is stablized, and the high advantage of specific capacitance can be used as a kind of electrode material of supercapacitor, when charging and discharging currents density is
When 0.5A/g, optimal specific capacitance reaches 750F/g, can supercapacitor, rechargeable battery field arrive large-scale application.
Specific case used herein elaborates inventive concept, the explanation of above example is only intended to
Help understands core of the invention thought.It should be pointed out that for those skilled in the art, not departing from this
Under the premise of inventive concept, any obvious modification, equivalent replacement or the other improvements made should be included in the present invention
Protection scope within.
Claims (6)
1. a kind of g-C3N4@NiCo2O4The preparation method of core-shell structure, which comprises the steps of:
(1) nickel foam is ultrasonically treated 20min in the hydrochloric acid solution of 0.1mol/L, removes the oxide on surface, cleaned and true
Sky is dry, is being 1: 2-3: 36 according to molar ratio, is weighing Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and urea respectively, dissolve
For solution in the mixed liquor of deionized water and dehydrated alcohol, the reaction density for controlling nickel nitrate is 0.05-0.1mol/L；
(2) processed nickel foam in step (1) and mixed liquor are transferred in reaction kettle simultaneously, 100~130 DEG C of reactions 8~
12h naturally cools to room temperature, and deionized water is washed 3 times, is dried to obtain NiCo2O4Presoma；
(3) it weighs and occupies NiCo obtained by step (2)2O4Presoma mass percent is the BA of 30%-50%, is configured to 0.1-
The BA ethanol solution of 0.3mol/L, by NiCo obtained in step (2)2O4Presoma is immersed in BA ethanol solution, obtains BA@
NiCo2O4Presoma；
(4) it weighs and occupies BA@NiCo obtained by step (3)2O4Presoma mass percent is the urea of 8%-20%, is dissolved in second
In alcohol, being made into concentration is 0.1-0.25mol/L solution, and by BA@NiCo2O4Presoma impregnates in urea liquid, dry, obtains
To urea@BA@NiCo2O4Presoma；
(5) step (4) is obtained into urea@BA@NiCo2O4Presoma obtains g-C in 300-325 DEG C of calcining 2-4h3N4@NiCo2O4
Core-shell structure.
2. a kind of g-C according to claim 13N4@NiCo2O4The preparation method of core-shell structure, which is characterized in that the step
Suddenly deionized water in the mixed liquor of deionized water and dehydrated alcohol in (1): dehydrated alcohol volume ratio is 1: 0.5-1.5.
3. a kind of g-C according to claim 13N4@NiCo2O4The preparation method of core-shell structure, which is characterized in that the step
Suddenly the molal weight of BA is 5.2-10.4mmol in (3).
4. a kind of g-C according to claim 33N4@NiCo2O4The preparation method of core-shell structure, which is characterized in that the step
Suddenly NiCo in (3)2O4Presoma soaking time in BA ethanol solution is 30-60min.
5. a kind of g-C according to claim 13N4@NiCo2O4The preparation method of core-shell structure, which is characterized in that the step
Suddenly BA@NiCo in (4)2O4Presoma soaking time in urea liquid is 20-30min.
6. a kind of g-C according to claim 13N4@NiCo2O4The preparation method of core-shell structure, which is characterized in that the step
Suddenly the g-C that (5) obtain3N4@NiCo2O4G-C in core-shell structure3N4With NiCo2O4Mass ratio be 0.05-0.1: 1.
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| CN113213555A (en) * | 2021-05-19 | 2021-08-06 | 国网天津市电力公司电力科学研究院 | Needle-like NiCo2O4Preparation method of super-electric material |
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