CN104900421A - Preparation method of nickel oxide/carbon sphere composite material - Google Patents
Preparation method of nickel oxide/carbon sphere composite material Download PDFInfo
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- CN104900421A CN104900421A CN201510190340.XA CN201510190340A CN104900421A CN 104900421 A CN104900421 A CN 104900421A CN 201510190340 A CN201510190340 A CN 201510190340A CN 104900421 A CN104900421 A CN 104900421A
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- nickel oxide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 147
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 54
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 239000011324 bead Substances 0.000 claims description 142
- 239000003513 alkali Substances 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003990 capacitor Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000003760 magnetic stirring Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- -1 metal oxide compound Chemical class 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- H01G11/32—Carbon-based
- H01G11/42—Powders or particles, e.g. composition thereof
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Microelectronics & Electronic Packaging (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A preparation method of a nickel oxide/carbon sphere composite material relates to the technical field of nano-material production. Backflow processing is carried out on ordered meso-pore carbon spheres, as carriers, in a NaOH solution, and a nickel hydroxide/carbon sphere precursor material is synthesized via hydrolysis of metal ions. The precursor is calcined in the atmosphere of nitrogen, nickel hydroxide is deposited to nickel oxide, and finally the nickel oxide/carbon sphere composite material is obtained. The preparation method provided by the invention is simple in technology and low in cost, and the prepared nickel oxide/carbon sphere composite material has good prospects in the field of super capacitors.
Description
Technical field
The present invention relates to the synthesis technical field of nano material, be specifically related to a kind of preparation method of mesoporous carbon back nickel oxide composite material.
Background technology
Meso-porous carbon material is widely used in the electrode material of ultracapacitor and battery because of its regular pore passage structure and larger pore capacities and good electric conductivity.But it has a major defect-energy density low as electrode material for super capacitor.How to improve its energy density and become one of focus of people's research.
According to energy theorem E=1/2CV
2known, the capacitive property improving electrode material can effectively improve its energy density.Nickel oxide is due to good electrochemical redox activity, and high theoretical ratio capacitance value and lower cost, obtain very large concern as fake capacitance material.But because its operating voltage is low, poorly conductive, actual performance is unsatisfactory.
Research shows, the composite material of material with carbon element and metal oxide compound gained not only has good conductivity but also have higher ratio capacitance performance.If material with carbon element and nickel oxide are combined with each other, can solve the problem that material with carbon element energy density is low, also can solve the shortcoming of nickel oxide poorly conductive, poor stability, the two synergy can show better chemical property.Therefore, the increasing researcher of composite quilt of porous carbon and nickel oxide pays close attention to, and expects the composite material obtaining excellent performance with low cost.
Summary of the invention
The present invention seeks to for the deficiencies in the prior art, provide that a kind of technique is simple, with low cost, the preparation method of the nickel oxide/carbon bead composite material with better chemical property.
The present invention includes following steps:
1) ordered mesopore carbon bead is carried out alkali reflow treatment in the NaOH aqueous solution, obtain the carbon bead of alkali treatment;
2) the carbon bead of alkali treatment is placed in nickel salt solution, through hydro-thermal reaction, obtains sized nickel hydroxide/carbon bead composite material precursor;
3) sized nickel hydroxide/carbon bead composite material precursor is calcined under an inert atmosphere, obtain nickel oxide/carbon bead composite material.
The carrier that the present invention selects in step 1) is ordered mesopore carbon bead, through carrying out alkali reflow treatment in the NaOH aqueous solution, obtains alkali treatment carbon bead; In step 2) in, through hydro-thermal reaction, utilize Hydrolysis Reactions of Metal-ions at carbon bead surface load hydrogen nickel oxide; Under the inert atmosphere of step 3) after calcining, obtain nickel oxide/carbon bead composite material.
Present invention process is simple, rationally, convenient production, preparing gained nickel oxide/carbon bead composite material is nucleocapsid structure, and particle diameter is 90-120nm, and load is at carbon bead surface equably for nickel oxide, and the nickel oxide thickness of deposition is 10 ~ 20nm.The specific area that can improve composite material of the mesoporous carbon bead in nickel oxide/carbon bead composite material and conductivity, and nickel oxide can provide high ratio capacitance value for composite material, the two plays synergy and makes composite material have better chemical property, has broad application prospects in ultracapacitor.
Further, in step 1), ordered mesopore carbon bead is dispersed in the NaOH aqueous solution, then room temperature is cooled to the condition lower magnetic force stirring and refluxing of 150 DEG C after 24 hours, again through centrifugal, taking precipitate ethanol and washed with de-ionized water, obtain the carbon bead of alkali treatment.If the alkali treatment time was more than 24 hours, then end product can be made overlapped, be formed crosslinked, cause the dispersiveness of sample to be deteriorated.
Be 6 M for disperseing the NaOH concentration of aqueous solution of ordered mesopore carbon bead.With 6 M NaOH mainly in order to provide enough-OH, carbon bead surface is made to modify one deck-OH.
During dispersion ordered mesopore carbon bead, first adopt magnetic agitation, then adopt ultrasonic.First adopt magnetic agitation to promote that carbon bead is evenly distributed in the solution, solution solubility gradient can not be caused; Then ultrasonic disperse can make carbon bead crosslinked together itself thoroughly scatter, and improves the monodispersity of carbon bead.
In step 2) in, the carbon bead of alkali treatment is dispersed in NiCl
2in the aqueous solution, after carrying out hydro-thermal reaction under 180 DEG C of conditions, be cooled to room temperature, through centrifugal, taking precipitate ethanol and washed with de-ionized water, then sediment is dry under 80 DEG C of vacuum conditions, obtain sized nickel hydroxide/carbon bead composite material precursor.Step of the present invention adopts hydro-thermal reaction, simple to operate, and course of reaction is easy to control, and the material crystal formation obtained is better.The material obtained is 80 DEG C of vacuumizes, and drying is relatively more thorough, noncrystalline water can be removed completely.
Dried product characteristics is stablized, and is easy to preserve and test.
When disperseing the carbon bead of alkali treatment, first adopt magnetic agitation, then adopt ultrasonic.First adopt magnetic agitation to promote that carbon bead is evenly distributed in the solution, solution solubility gradient can not be caused; Then ultrasonic disperse can make carbon bead crosslinked together thoroughly scatter, and improves the monodispersity of carbon bead.
For disperseing the NiCl of the carbon bead of described alkali treatment
2the concentration of the aqueous solution is 0.1 ~ 0.2 M.Under this concentration, Ni
2+basic load at carbon bead surface, and self is not easy to produce reunion.
In addition, the carbon bead of alkali treatment and the rate of charge of nickel salt solution are 0.075g:20mL.Under this rate of charge, nickel oxide can all uniform load be at carbon bead surface, and obtain the nickel oxide/carbon bead composite material of nucleocapsid structure, sample can not be cross-linked, and monodispersity is better.
In step 3), rise to 350 DEG C during calcining with the programming rate of 5 DEG C/min, constant temperature stops heating after 2 hours.Heat up with the programming rate of 5 DEG C/min, homogenize material can be made to heat, nickel hydroxide decomposition obtains the good nickel oxide of crystal formation.If heating rate is too fast, can accelerate the decomposition rate of nickel hydroxide, the comparatively loose crystal formation of the nickel oxide structure obtained is poor, and sample is easily cross-linked, and reunites more serious.Nickel hydroxide 350 DEG C time for nickel oxide can be decomposed into, when calcining heat can not be decomposed lower than nickel hydroxide when 350 DEG C, when calcining heat is higher than 350 DEG C, nickel oxide can be reduced into nickel by material with carbon element, therefore only calcine at 350 DEG C, just can obtain the good nickel oxide of crystal formation/carbon bead composite material.As calcination time is less than 2 hours, nickel hydroxide decomposes not exclusively; As calcination time is greater than 2 hours, can cause the wasting of resources, constantly little in calcining 2, nickel hydroxide is all decomposed into nickel oxide.
Described inert atmosphere is N
2atmosphere.The present invention N2, as protective gas, can completely cut off air, to prevent in composite material carbon bead by the oxygen high-temperature oxydation in air.And N2 is relative to other protective gas, there is cheap, to be easy to storage feature.
Accompanying drawing explanation
Fig. 1 schemes through the TEM of the carrier mesoporous carbon bead of alkali treatment in embodiment 1,2,3, and scale is 200 nm.
Fig. 2 is the TEM figure that embodiment 1,2,3 prepares the presoma sized nickel hydroxide/carbon bead composite material of gained, and scale is 100 nm.
Fig. 3 is the TEM figure that embodiment 1 prepares the nickel oxide/carbon bead composite material of gained, and scale is 200 nm.
Fig. 4 is the TEM figure that embodiment 2 prepares the nickel oxide/carbon bead composite material of gained, and scale is 200nm.
Fig. 5 is the TEM figure that embodiment 3 prepares the nickel oxide/carbon bead composite material of gained, and scale is 200nm.
Fig. 6 is the TEM figure that embodiment 4 prepares the nickel oxide hollow ball of gained, and scale is 100nm.
Fig. 7 is X-ray diffraction (XRD) figure of the alkali treatment carbon bead of embodiment 1 gained.
Fig. 8 is X-ray diffraction (XRD) figure that embodiment 3 prepares the nickel oxide/carbon bead composite material of gained.
Embodiment
Term used in the present invention, unless otherwise specified, generally has the implication that those of ordinary skill in the art understand usually.
Below in conjunction with specific embodiment, and comparable data describes the present invention in further detail.Should be understood that these embodiments just in order to demonstrate the invention, but not limit the scope of the invention by any way.
Below in an example, the various process do not described in detail and method are conventional methods as known in the art.
Embodiment 1:
1, the alkali treatment of ordered mesopore carbon bead: add in the round-bottomed flask that 50mL 6M NaOH solution is housed by 0.1g mesoporous carbon bead, magnetic stirring apparatus stirs 10 minutes, and then ultrasonic disperse 20 minutes, makes carbon bead in the solution dispersed.Room temperature is naturally cooled to after 24 hours 150 DEG C of heating condition lower magnetic force stirring and refluxing; Then reaction system centrifugal after be precipitated, then as cleaning solution, centrifuge washing is carried out for several times to gained precipitation using deionized water, ethanol, then by the vacuumize of gained sediment, obtains alkali treatment carbon bead.
Carrier carbon bead as shown in Figure 1.As seen from Figure 1: ordered mesopore carbon bead presents homogeneous nanometer spherical morphology, and regular pore passage structure, monodispersity is better.
2, the preparation of sized nickel hydroxide/carbon bead composite material precursor: first prepare 20mL 0.1M NiCl
2the aqueous solution.In this aqueous solution, add 0.075g alkali treatment carbon bead, magnetic stirring apparatus stirs 10 minutes, more ultrasonic 20 minutes allow carbon bead be uniformly dispersed.Be transferred to by aggregate sample in polytetrafluoroethyl-ne alkene reaction in still, be placed in stainless steel cauldron, at 180 DEG C, hydro-thermal reaction took out reactor after 24 hours, naturally cooled to room temperature.Collected by centrifugation black precipitate, with ethanol and water washing several.Be deposited in drying in 80 DEG C of vacuum drying chambers and within 6 hours, namely obtain presoma sized nickel hydroxide/carbon bead composite material, i.e. the bead of sized nickel hydroxide/carbon shown in Fig. 2 composite material.
By transmission electron microscope (TEM) observe, presoma maintains the nanometer chondritic of carbon bead masterplate, and the presoma preparing gained is nucleocapsid structure, nickel hydroxide in the form of sheets load at carbon bead surface.
The preparation of 3, nickel oxide/carbon bead: the sized nickel hydroxide/carbon bead presoma of preparation is placed in tube furnace, at N
2rise to 350 DEG C with the programming rate of 5 DEG C/min in atmosphere, constant temperature stops heating after 2 hours.Treat that tube furnace is cooled to room temperature, open tube furnace and take out wherein black solid and be nickel oxide/carbon bead composite material, i.e. nickel oxide shown in Fig. 3/carbon bead composite material.
Observe known by transmission electron microscope (TEM), prepare gained composites and maintain the nanometer chondritic of carbon bead masterplate and for nucleocapsid structure, hydroxide flake nickel is decomposed into particulate oxidation nickel uniform load at carbon bead surface.Composite material monodispersity is better.
Embodiment 2:
1, the alkali treatment of ordered mesopore carbon bead: added by 0.1g mesoporous carbon bead in the round-bottomed flask that 50 mL6 M NaOH solution are housed, magnetic stirring apparatus stirs 10 minutes, and then ultrasonic disperse 20 minutes, makes carbon bead in the solution dispersed.Room temperature is naturally cooled to after 24 hours 150 DEG C of condition lower magnetic force stirring and refluxing; Then reaction system centrifugal after be precipitated, then carry out centrifuge washing for several times using deionized water, ethanol as cleaning solution, by the vacuumize of gained sediment, obtain alkali treatment carbon bead.
Carrier carbon bead as shown in Figure 1.As seen from Figure 1: ordered mesopore carbon bead presents homogeneous nanometer spherical morphology, and regular pore passage structure, monodispersity is better.
2, the preparation of sized nickel hydroxide/carbon bead composite material precursor: first prepare 20mL 0.15M NiCl
2the aqueous solution.In this aqueous solution, add 0.075g alkali treatment carbon bead, magnetic stirring apparatus stirs 10 minutes, more ultrasonic 20 minutes allow carbon bead be uniformly dispersed.Be transferred to by aggregate sample in polytetrafluoroethyl-ne alkene reaction in still, be placed in stainless steel cauldron, at 180 DEG C, hydro-thermal reaction took out reactor after 24 hours, naturally cooled to room temperature.Collected by centrifugation black precipitate, with ethanol and water washing several.To be deposited in 80 DEG C of vacuum drying chambers dry 6 hours presoma sized nickel hydroxide/carbon bead composite material, i.e. the bead of sized nickel hydroxide/carbon shown in Fig. 2 composite material.
Observed by transmission electron microscope (TEM), presoma maintains the nanometer chondritic of carbon bead masterplate, and the presoma made is nucleocapsid structure, and the load of nickel hydroxide slabbing is at carbon bead surface.
The preparation of 3, nickel oxide/carbon bead: the sized nickel hydroxide/carbon bead presoma of preparation is placed in tube furnace, at N
2in atmosphere, rise to 350 DEG C with the programming rate of 5 DEG C/min, constant temperature stops heating after 2 hours, treat that tube furnace is cooled to room temperature, opens tube furnace and takes out wherein black solid and be nickel oxide/carbon bead composite material, i.e. nickel oxide shown in Fig. 4/carbon bead composite material.
Observed by transmission electron microscope (TEM), gained composites maintains the nanometer chondritic of carbon bead masterplate and is nucleocapsid structure, and hydroxide flake nickel is decomposed into nickel oxide particle uniform load at carbon bead surface.Composite material monodispersity is better.
Embodiment 3:
1, the alkali treatment of ordered mesopore carbon bead: add in the round-bottomed flask that 50mL 6M NaOH solution is housed by 0.1g mesoporous carbon bead, magnetic stirring apparatus stirs 10 minutes, and then ultrasonic disperse 20 minutes, makes carbon bead in the solution dispersed.Room temperature is naturally cooled to after 24 hours 150 DEG C of condition lower magnetic force stirring and refluxing; Then reaction system centrifugal after be precipitated, then carry out centrifuge washing for several times using deionized water, ethanol as cleaning solution, by the vacuumize of gained sediment, obtain alkali treatment carbon bead.
Carrier carbon bead as shown in Figure 1.As seen from Figure 1: ordered mesopore carbon bead presents homogeneous nanometer spherical morphology, and regular pore passage structure, monodispersity is better.
2, the preparation of sized nickel hydroxide/carbon bead composite material precursor: the NiCl first preparing 20mL 0.2M
2the aqueous solution.In this aqueous solution, add 0.075g alkali treatment carbon bead, magnetic stirring apparatus stirs 10 minutes, more ultrasonic 20 minutes allow carbon bead be uniformly dispersed.Be transferred to by aggregate sample in polytetrafluoroethyl-ne alkene reaction in still, be placed in stainless steel cauldron, at 180 DEG C, hydro-thermal reaction took out reactor after 24 hours, naturally cooled to room temperature.Collected by centrifugation black precipitate, with ethanol and water washing several.To be deposited in 80 DEG C of vacuum drying chambers dry 6 hours presoma sized nickel hydroxide/carbon bead composite material, i.e. the bead of sized nickel hydroxide/carbon shown in Fig. 2 composite material.
Observed by transmission electron microscope (TEM), presoma maintains the nanometer chondritic of carbon bead masterplate, and the presoma made is nucleocapsid structure, and the load of nickel hydroxide slabbing is at carbon bead surface.
The preparation of 3, nickel oxide/carbon bead: the sized nickel hydroxide/carbon bead presoma of preparation is placed in tube furnace, at N
2in atmosphere, rise to 350 DEG C with the programming rate of 5 DEG C/min, constant temperature stops heating after 2 hours, treat that tube furnace is cooled to room temperature, opens tube furnace and takes out wherein black solid and be nickel oxide/carbon bead composite material, i.e. nickel oxide shown in Fig. 5/carbon bead composite material.
Embodiment 4:
1, the alkali treatment of ordered mesopore carbon bead: add in the round-bottomed flask that 50mL 6M NaOH solution is housed by 0.1g mesoporous carbon bead, magnetic stirring apparatus stirs 10 minutes, and then ultrasonic disperse 20 minutes, makes carbon bead in the solution dispersed.Room temperature is naturally cooled to after 24 hours 150 DEG C of condition lower magnetic force stirring and refluxing; Then reaction system centrifugal after be precipitated, then carry out centrifuge washing for several times using deionized water, ethanol as cleaning solution, by the vacuumize of gained sediment, obtain alkali treatment carbon bead.Carrier carbon bead as shown in Figure 1.
As seen from Figure 1: ordered mesopore carbon bead presents homogeneous nanometer spherical morphology, and regular pore passage structure, monodispersity is better.
2, the preparation of sized nickel hydroxide/carbon bead composite material precursor: the NiCl first preparing 20mL 0.2M
2the aqueous solution.In this aqueous solution, add 0.075g alkali treatment carbon bead, magnetic stirring apparatus stirs 10 minutes, more ultrasonic 20 minutes allow carbon bead be uniformly dispersed.Be transferred to by aggregate sample in polytetrafluoroethyl-ne alkene reaction in still, be placed in stainless steel cauldron, at 180 DEG C, hydro-thermal reaction took out reactor after 24 hours, naturally cooled to room temperature.Collected by centrifugation black precipitate, with ethanol and water washing several.To be deposited in 80 DEG C of vacuum drying chambers dry 6 hours presoma sized nickel hydroxide/carbon bead composite material, i.e. the bead of sized nickel hydroxide/carbon shown in Fig. 2 composite material.
Observed by transmission electron microscope (TEM), presoma maintains the nanometer chondritic of carbon bead masterplate, and the presoma made is nucleocapsid structure, and the load of nickel hydroxide slabbing is at carbon bead surface.
The preparation of 3, nickel oxide/carbon bead: the sized nickel hydroxide/carbon bead presoma of preparation is placed in tube furnace, in air atmosphere, 350 DEG C are risen to the programming rate of 5 DEG C/min, constant temperature stops heating after 2 hours, treat that tube furnace is cooled to room temperature, open tube furnace to take out wherein black solid and be nickel oxide/carbon bead composite material, i.e. the TEM figure of the hollow ball of nickel oxide shown in Fig. 6.
Observed by transmission electron microscope (TEM), gained composites maintains the nanometer chondritic of carbon bead masterplate and is nucleocapsid structure, hydroxide flake nickel is decomposed into nickel oxide particle uniform load at carbon bead surface, and composite material monodispersity is better.
As can be seen from enforcement 1,2,3 and Fig. 3,4,5, along with NiCl
2the increase of consumption, load is also increasing in the NiO amount of carbon bead surface.Illustrate that the present invention can simply by control NiCl
2consumption control the load capacity of carbon bead surface NiO.
As can be seen from enforcement 3,4 and Fig. 5,6, when calcining, the existence of nitrogen effectively protects the oxidized decomposition of carbon bead, contributes to obtaining nickel oxide/carbon bead composite material.
The product of embodiment 1-3, through XRD determining, confirms in composite material containing nickel oxide.For embodiment 3 product, the XRD collection of illustrative plates of embodiment 3 product is as Fig. 7.
Fig. 7 is carbon bead XRD collection of illustrative plates.As seen from the figure, its characteristic peak appear at respectively 2 θ=24.5 °, 43.2 °, correspond respectively to (002) and (100) crystal face of carbon, illustrate that the degree of graphitization of carbon bead is higher.Fig. 8 is the XRD figure of nickel oxide/carbon bead composite material.As seen from the figure, sample is 37.2 ° at 2 θ, 43.3 °, 62.8 °, there is obvious characteristic diffraction peak at 75.3 ° and 79.3 ° of places, contrast standard card, corresponds respectively to (001) of nickel oxide, (200), (111), (312) and (002) crystal face, show that the material being coated on carbon bead surface is nickel oxide, further illustrating this composite material is nickel oxide/carbon bead composite material.
Claims (10)
1. a preparation method for nickel oxide/carbon bead composite material, is characterized in that comprising the following steps:
1) ordered mesopore carbon bead is carried out alkali reflow treatment in the NaOH aqueous solution, obtain the carbon bead of alkali treatment;
2) the carbon bead of alkali treatment is placed in nickel salt solution, through hydro-thermal reaction, obtains sized nickel hydroxide/carbon bead composite material precursor;
3) sized nickel hydroxide/carbon bead composite material precursor is calcined under an inert atmosphere, obtain nickel oxide/carbon bead composite material.
2. preparation method according to claim 1, it is characterized in that in described step 1), ordered mesopore carbon bead is dispersed in the NaOH aqueous solution, then room temperature is cooled to the condition lower magnetic force stirring and refluxing of 150 DEG C after 24 hours, again through centrifugal, taking precipitate ethanol and washed with de-ionized water, obtain the carbon bead of alkali treatment.
3. preparation method according to claim 2, is characterized in that in described step 1), is 6 M for disperseing the NaOH concentration of aqueous solution of ordered mesopore carbon bead.
4. the preparation method according to Claims 2 or 3, is characterized in that in described step 1), during dispersion ordered mesopore carbon bead, first adopts magnetic agitation, then adopts ultrasonic.
5. preparation method according to claim 1, is characterized in that described step 2) in, the carbon bead of alkali treatment is dispersed in NiCl
2in the aqueous solution, after carrying out hydro-thermal reaction under 180 DEG C of conditions, be cooled to room temperature, through centrifugal, taking precipitate ethanol and washed with de-ionized water, then sediment is dry under 80 DEG C of vacuum conditions, obtain sized nickel hydroxide/carbon bead composite material precursor.
6. preparation method according to claim 5, is characterized in that described step 2) in, when disperseing the carbon bead of alkali treatment, first adopt magnetic agitation, then adopt ultrasonic.
7. preparation method according to claim 5, is characterized in that described step 2) in, for disperseing the NiCl of the carbon bead of described alkali treatment
2the concentration of the aqueous solution is 0.1 ~ 0.2 M.
8. preparation method according to claim 5, is characterized in that described step 2) in, the carbon bead of alkali treatment and the rate of charge of nickel salt solution are 0.075g:20mL.
9. preparation method according to claim 1, is characterized in that, in described step 3), rising to 350 DEG C during calcining with the programming rate of 5 DEG C/min, and constant temperature stops heating after 2 hours.
10. the preparation method according to claim 1 or 9, is characterized in that in described step 3), and described inert atmosphere is N
2atmosphere.
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| CN105702484A (en) * | 2016-01-27 | 2016-06-22 | 同济大学 | A manufacturing method for a NiO/mesoporous carbon nanosphere which is supercapacitor electrode materials |
| CN107204450A (en) * | 2017-06-30 | 2017-09-26 | 吉林大学 | The preparation method and applications of nickel oxide nanoparticle/carbon nanometer helmet composite (NiO/CNHs) |
| CN110828190A (en) * | 2018-08-10 | 2020-02-21 | 南京理工大学 | Hollow mesoporous carbon sphere @ nickel hydroxide nanocomposite and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105702484A (en) * | 2016-01-27 | 2016-06-22 | 同济大学 | A manufacturing method for a NiO/mesoporous carbon nanosphere which is supercapacitor electrode materials |
| CN105702484B (en) * | 2016-01-27 | 2017-12-26 | 同济大学 | A kind of preparation method of the mesoporous Nano carbon balls of electrode material for super capacitor NiO/ |
| CN107204450A (en) * | 2017-06-30 | 2017-09-26 | 吉林大学 | The preparation method and applications of nickel oxide nanoparticle/carbon nanometer helmet composite (NiO/CNHs) |
| CN107204450B (en) * | 2017-06-30 | 2019-10-22 | 吉林大学 | Nickel oxide nanoparticle/carbon nanometer helmet composite material preparation method and applications |
| CN110828190A (en) * | 2018-08-10 | 2020-02-21 | 南京理工大学 | Hollow mesoporous carbon sphere @ nickel hydroxide nanocomposite and preparation method thereof |
| CN110828190B (en) * | 2018-08-10 | 2022-02-18 | 南京理工大学 | Hollow mesoporous carbon sphere @ nickel hydroxide nanocomposite and preparation method thereof |
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