CN107195483A - A kind of preparation method of the NiO/ Nano carbon balls with core shell structure - Google Patents
A kind of preparation method of the NiO/ Nano carbon balls with core shell structure Download PDFInfo
- Publication number
- CN107195483A CN107195483A CN201710320025.3A CN201710320025A CN107195483A CN 107195483 A CN107195483 A CN 107195483A CN 201710320025 A CN201710320025 A CN 201710320025A CN 107195483 A CN107195483 A CN 107195483A
- Authority
- CN
- China
- Prior art keywords
- nio
- shell structure
- core shell
- sio
- nano carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 241000143432 Daldinia concentrica Species 0.000 title claims abstract description 28
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 28
- 239000011258 core-shell material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 32
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- 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 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052681 coesite Inorganic materials 0.000 claims description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 229910052682 stishovite Inorganic materials 0.000 claims description 16
- 229910052905 tridymite Inorganic materials 0.000 claims description 16
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 239000002114 nanocomposite Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 9
- 239000003990 capacitor Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 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
- H01G11/84—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
-
- 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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Nanotechnology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Carbon And Carbon Compounds (AREA)
- Composite Materials (AREA)
Abstract
The present invention relates to a kind of preparation method of the NiO/ Nano carbon balls with core shell structure.By 0.3~1.2：100：31.6：0.05~0.25：4.7：1.4：1：1 quality parts ratio measures ammoniacal liquor, water, absolute ethyl alcohol, Nickelous nitrate hexahydrate, tetraethyl orthosilicate, formalin, resorcinol and cetyl trimethylammonium bromide, by ammoniacal liquor, water and absolute ethyl alcohol add Nickelous nitrate hexahydrate after mixing, stir 10~120min, sequentially add resorcinol and cetyl trimethylammonium bromide, stir and formalin and tetraethyl orthosilicate are added after 30min, stir 24h after at 100 DEG C hydro-thermal reaction 24h, then it is placed in tube furnace, under nitrogen atmosphere, 1~10 DEG C/min heating rate is from room temperature to 700~900 DEG C of carbonizations, the NaOH solution for being finally 3mol/L with concentration removes the SiO in product2, obtain the NiO/ Nano carbon balls with core shell structure；Present invention process is simple, easy to operate, during as electrode material for super capacitor, shows higher specific capacitance and preferable cyclical stability.
Description
Technical field
The present invention relates to a kind of preparation method of the NiO/ Nano carbon balls with core shell structure, belong to material preparation technology neck
Domain.
Background technology
Energy problem receives significant attention in recent years, and ultracapacitor is because its is environment-friendly, the spy that has extended cycle life etc.
Point, there is good application prospect in terms of energy automobile and consumer electronics product.Porous carbon materials are because of its specific surface area
The advantages of height, good conductivity, Stability Analysis of Structures, is as the electrode material for super capacitor for applying more, but porous carbon materials are deposited
In the not high shortcoming of specific capacitance.Comparatively, transition metal oxide such as nickel oxide, manganese oxide etc., with cheap, raw material
The advantages of wide material sources, high specific capacitance, but there is also the deficiencies such as cyclical stability difference simultaneously.Therefore, transiting metal oxidation is studied
Thing/carbon composite, the two advantage is combined, and is a focus of current electrode material for super capacitor research.For example, " one
Plant the preparation method of oxidation nickel carbon bead composite " (Chinese invention patent, application number：201510190340.X) with orderly
Mesoporous carbon bead is carrier, and reflow treatment is carried out first in NaOH solution, then obtains hydrogen using Hydrolysis Reactions of Metal-ions synthesis
Nickel carbon bead is aoxidized, heat treatment is finally combined, oxidation nickel carbon bead composite has been made.A kind of " electrode of super capacitor
The preparation method of the mesoporous Nano carbon balls of material Ni O/ " (Chinese invention patent, application number：201610055611.5) it is first by SiO2
Colloidal sol after nickel salt stirring, hydro-thermal with obtaining NiO/SiO2Nano-particle, then again to obtained NiO/SiO2Added in nano-particle
Resorcinol and formalin, are again stirring for, obtain containing NiO/SiO after hydro-thermal process2Polymer nanocomposite ball, last carbon
Change, remove SiO2The mesoporous Nano carbon balls of NiO/ are obtained after template.However, to there is preparation method more multiple for these microballoon composites
Miscellaneous the shortcomings of, as the former needs reflow treatment, the latter needs two step hydro-thermals, and these all improve technology difficulty and complex operation journey
Degree.
The content of the invention
It is an object of the invention to disclose a kind of preparation method of the NiO/ Nano carbon balls with core shell structure.Use this method
The NiO/ Nano carbon balls electrode materials with core shell structure prepared, simple with preparation technology, specific capacitance is high, cyclical stability
Can be good the advantages of.
To reach above-mentioned purpose, Nickelous nitrate hexahydrate is first distributed to three solution bodies of ammoniacal liquor, absolute ethyl alcohol, water by the present invention
Nickel ammonia chelate is formed in system, in the hydrolysis of follow-up tetraethyl orthosilicate, polymerization and resorcinol and oxymethylene polymerization process
In, nickel ammonia chelate is by SiO2Nano-particle parcel is distributed in core-shell polymer nanosphere, through carbonization, removes SiO2After obtain
NiO/ Nano carbon balls.The specific capacitance of composite can be greatly improved in the fake capacitance that NiO is brought, with mesoporous, microcellular structure carbon
Shell, can effectively prevent NiO seepages, and improve the stable circulation performance of electrode material.
Concrete technology is carried out as follows：
By 0.3~1.2：100：31.6：0.05~0.25：4.7：1.4：1：1 quality parts ratio measures ammoniacal liquor, water, anhydrous
Ethanol, Nickelous nitrate hexahydrate, tetraethyl orthosilicate, formalin, resorcinol and cetyl trimethylammonium bromide, first by ammonia
Water, water and absolute ethyl alcohol are well mixed, add Nickelous nitrate hexahydrate and stir 10~120min, sequentially add resorcinol and 16
Alkyl trimethyl ammonium bromide, continues to stir 30min, then adds after formalin and tetraethyl orthosilicate, stirring 24h 100
Hydro-thermal reaction 24h at DEG C, obtains containing NiO and SiO2The polymer nanocomposite ball of nano-particle；It is placed in tube furnace, in nitrogen
Under atmosphere, 1~10 DEG C/min heating rate, from room temperature to 700~900 DEG C of carbonizations, is finally 3mol/L's with concentration
NaOH solution removes the SiO in product2, obtain the NiO/ Nano carbon balls with core shell structure；
Above raw material is commercially available technical grade product.
The consumption of wherein NaOH solution is the SiO in product212 times of quality.
Analysis test result shows that gained has the NiO/ Nano carbon balls of core shell structure uniform in size, good dispersion, diameter
About 600nm, specific surface area 750m2/ more than g.
The invention has the advantages that：
1. Nickelous nitrate hexahydrate is first dispersed in formation nickel ammonia in three solution systems of ammoniacal liquor, absolute ethyl alcohol and water by this method
Chelate, nickel ammonia chelate is by SiO in the hydrolysis of tetraethyl orthosilicate and polymerization process2Nano-particle is wrapped up, and can prevent NiO
Assemble and reduced by carbon material during high temperature cabonization, and can effectively prevent the reunion of NiO nano-particles, NiO quilts can be made
The NiO/ Nano carbon balls with core shell structure uniformly coated.
What 2. the present invention was obtained contains NiO and SiO2The polymer nanocomposite ball of nano-particle, through carbonization, removes SiO2After obtain
The specific capacitance of composite can be greatly improved in NiO/ Nano carbon balls, the fake capacitance that NiO is brought, with mesoporous, microcellular structure carbon
Shell, can effectively prevent NiO seepages, and improve the stable circulation performance of electrode material.
3. the present invention is prepared by one-step method only to be needed once in the NiO/ Nano carbon balls with core shell structure, preparation process
Hydro-thermal and once it is carbonized, has the advantages that technique is simple, operating process is easy.
4. the NiO/ Nano carbon balls with core shell structure prepared by the present invention are uniform in size, good dispersion, diameter is about
600nm, specific surface area 750m2/ more than g.When NiO/ Nano carbon balls with core shell structure are as electrode material for super capacitor,
Analysis and tests show that, under 1.0A/g during discharge and recharge, its specific capacitance reaches the appearance after more than 350F/g, cycle charge-discharge 5000 times
Conservation rate is measured more than 90%, higher specific capacitance and preferable cyclical stability is shown.
Embodiment
Embodiment 1
By 0.3：100：31.6：0.05：4.7：1.4：1：1 quality parts ratio measures ammoniacal liquor, water, absolute ethyl alcohol, six hydrations
Nickel nitrate, tetraethyl orthosilicate, formalin, resorcinol and cetyl trimethylammonium bromide, first by ammoniacal liquor, water and anhydrous
Ethanol is well mixed, and adds Nickelous nitrate hexahydrate, is stirred 10min, is sequentially added resorcinol and cetyl trimethyl bromination
Ammonium, continues to stir 30min, then adds after formalin and tetraethyl orthosilicate, stirring 24h the hydro-thermal reaction at 100 DEG C
24h, obtains containing NiO and SiO2The polymer nanocomposite ball of nano-particle.It is placed in tube furnace, under nitrogen atmosphere, 1 DEG C/
Min heating rate is finally removed in product from room temperature to 700 DEG C of carbonizations with the NaOH solution that concentration is 3mol/L
SiO2, obtain the NiO/ Nano carbon balls with core shell structure.The consumption of above-mentioned NaOH solution is the SiO in product2The 12 of quality
Times.
Embodiment 2
By 0.6：100：31.6：0.1：4.7：1.4：1：1 quality parts ratio measures ammoniacal liquor, water, absolute ethyl alcohol, six hydration nitre
Sour nickel, tetraethyl orthosilicate, formalin, resorcinol and cetyl trimethylammonium bromide, first by ammoniacal liquor, water and anhydrous second
Alcohol is well mixed, and adds Nickelous nitrate hexahydrate, is stirred 30min, is sequentially added resorcinol and cetyl trimethylammonium bromide,
Continue to stir 30min, then add after formalin and tetraethyl orthosilicate, stirring 24h the hydro-thermal reaction 24h at 100 DEG C, obtain
To containing NiO and SiO2The polymer nanocomposite ball of nano-particle.It is placed in tube furnace, under nitrogen atmosphere, 4 DEG C/min liter
Warm speed is from room temperature to 750 DEG C of charings, and the NaOH solution for being finally 3mol/L with concentration removes the SiO in product2, obtain
NiO/ Nano carbon balls with core shell structure；The consumption of above-mentioned NaOH solution is the SiO in product212 times of quality.
Embodiment 3
By 0.9：100：31.6：0.2：4.7：1.4：1：1 quality parts ratio measures ammoniacal liquor, water, absolute ethyl alcohol, six hydration nitre
Sour nickel, tetraethyl orthosilicate, formalin, resorcinol and cetyl trimethylammonium bromide, first by ammoniacal liquor, water and anhydrous second
Alcohol is well mixed, and adds Nickelous nitrate hexahydrate, is stirred 80min, is sequentially added resorcinol and cetyl trimethylammonium bromide,
Continue to stir 30min, then add after formalin and tetraethyl orthosilicate, stirring 24h the hydro-thermal reaction 24h at 100 DEG C, obtain
To containing NiO and SiO2The polymer nanocomposite ball of nano-particle.It is placed in tube furnace, under nitrogen atmosphere, 8 DEG C/min liter
Warm speed is from room temperature to 800 DEG C of carbonizations, and the NaOH solution for being finally 3mol/L with concentration removes the SiO in product2, obtain
NiO/ Nano carbon balls with core shell structure.The consumption of above-mentioned NaOH solution is the SiO in product212 times of quality.
Embodiment 4
By 1.2：100：31.6：0.25：4.7：1.4：1：1 quality parts ratio measures ammoniacal liquor, water, absolute ethyl alcohol, six hydrations
Nickel nitrate, tetraethyl orthosilicate, formalin, resorcinol and cetyl trimethylammonium bromide, first by ammoniacal liquor, water and anhydrous
Ethanol is well mixed, and adds Nickelous nitrate hexahydrate, is stirred 120min, is sequentially added resorcinol and cetyl trimethyl bromination
Ammonium, continues to stir 30min, then adds after formalin and tetraethyl orthosilicate, stirring 24h the hydro-thermal reaction at 100 DEG C
24h, obtains containing NiO and SiO2The polymer nanocomposite ball of nano-particle.It is placed in tube furnace, under nitrogen atmosphere, 10 DEG C/
Min heating rate is finally removed in product from room temperature to 900 DEG C of carbonizations with the NaOH solution that concentration is 3mol/L
SiO2, obtain the NiO/ Nano carbon balls with core shell structure.The consumption of NaOH solution is the SiO in product212 times of quality.
Analysis test result shows that the NiO/ Nano carbon balls with core shell structure that embodiment 1-4 is obtained are uniform in size, point
Dissipate property good, diameter about 600nm, specific surface area 750m2/ more than g.The NiO/ carbon with core shell structure that embodiment 1-4 is obtained
Nanosphere presses 8 with graphite and polytetrafluoroethylene (PTFE)：1：1 mass ratio is measured, and is dissolved in after ground and mixed is uniform in ethanol solution, ultrasound
Vibrate 1h formation slurries.The slurry is uniformly coated in nickel foam, and obtained in 80 DEG C of oven drying 24h with nucleocapsid
The NiO/ Nano carbon balls electrode material for super capacitor of structure.Using the NiO/ Nano carbon balls with core shell structure as working electrode,
Nickel foam is that, to electrode, Hg/HgO electrodes are reference electrode.KOH with electrochemical workstation (CHI 660D) in 6mol/L is electrolysed
In liquid, in 25 DEG C of specific capacitance values in potential window -1.0~NiO/ Nano carbon balls electrode material of the 0V tests with core shell structure
With cycle charge discharge electrical property.Test result shows that gained has the NiO/ Nano carbon balls of core shell structure as super capacitor electrode
Pole material, under 1.0A/g during discharge and recharge, the capability retention that specific capacitance reaches after more than 350F/g, cycle charge-discharge 5000 times exists
More than 90%, show higher specific capacitance and preferable cyclical stability.
Above raw material is commercially available technical grade product.
Above-mentioned hydro-thermal reaction refers to：Reactant is fitted into the stainless steel water heating kettle of inner liner polytetrafluoroethylene and carried out at hydro-thermal
Reason reaction.
Claims (1)
1. a kind of preparation method of the NiO/ Nano carbon balls with core shell structure, it is characterised in that：Ammonia is measured by quality parts ratio
Water：Water：Absolute ethyl alcohol：Nickelous nitrate hexahydrate：Tetraethyl orthosilicate：Formalin：Resorcinol：Cetyl trimethyl bromination
Ammonium=0.3~1.2：100：31.6：0.05~0.25：4.7：1.4：1：1, then, ammoniacal liquor, water and absolute ethyl alcohol are first mixed equal
It is even, Nickelous nitrate hexahydrate is added, 10~120min is stirred, sequentially adds resorcinol and cetyl trimethylammonium bromide,
Continue to stir 30min, then add formalin and tetraethyl orthosilicate, be stirred for after 24h the hydro-thermal reaction 24h at 100 DEG C,
Obtain containing NiO and SiO2The polymer nanocomposite ball of nano-particle, is placed in tube furnace, under nitrogen atmosphere, with 1~10
DEG C/min heating rate from room temperature to 700~900 DEG C of carbonizations, the NaOH solution for being finally 3mol/L with concentration removes production
SiO in thing2, obtain the NiO/ Nano carbon balls with core shell structure；
Above-mentioned hydro-thermal reaction refers to：Reactant is fitted into progress hydro-thermal process in the stainless steel water heating kettle of inner liner polytetrafluoroethylene anti-
Should；
The consumption of above-mentioned NaOH solution is the SiO in product212 times of quality；
Above-mentioned raw materials are commercially available technical grade product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710320025.3A CN107195483B (en) | 2017-05-09 | 2017-05-09 | A kind of preparation method of the NiO/ Nano carbon balls with nucleocapsid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710320025.3A CN107195483B (en) | 2017-05-09 | 2017-05-09 | A kind of preparation method of the NiO/ Nano carbon balls with nucleocapsid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107195483A true CN107195483A (en) | 2017-09-22 |
| CN107195483B CN107195483B (en) | 2018-09-14 |
Family
ID=59873810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710320025.3A Expired - Fee Related CN107195483B (en) | 2017-05-09 | 2017-05-09 | A kind of preparation method of the NiO/ Nano carbon balls with nucleocapsid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107195483B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108232167A (en) * | 2018-01-19 | 2018-06-29 | 洛阳理工学院 | A kind of carbon@ferrosilites hollow-core construction compound and preparation method thereof |
| CN109985643A (en) * | 2019-03-19 | 2019-07-09 | 贵州大学 | A kind of add in-place bromine preparation small size PdKBrThe method of@HSC |
| 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 |
| CN111377431A (en) * | 2020-03-19 | 2020-07-07 | 上海交通大学 | Morphology-controllable-adjustable nitrogen-loaded carbon nanocapsule and preparation method and application thereof |
| CN113096966A (en) * | 2021-04-16 | 2021-07-09 | 广德天运新技术股份有限公司 | High-specific-capacity supercapacitor electrode material based on silicon dioxide and preparation method thereof |
| CN114583140A (en) * | 2022-05-05 | 2022-06-03 | 潍坊科技学院 | Nickel disulfide/silicon composite material with core-shell structure and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103427073A (en) * | 2013-08-05 | 2013-12-04 | 同济大学 | Preparation method of mesoporous Si/C composite microsphere as lithium battery negative electrode material |
| CN105217601A (en) * | 2015-11-05 | 2016-01-06 | 北京工业大学 | A kind of preparation method with the porous hollow carbon ball of high-specific surface area |
| 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 |
| CN105752966A (en) * | 2016-01-27 | 2016-07-13 | 同济大学 | Preparation method of graphene/hollow carbon nanometer balls |
| CN105819422A (en) * | 2016-03-17 | 2016-08-03 | 南京理工大学 | Preparation method of nitrogen doped hollow mesoporous carbon sphere |
-
2017
- 2017-05-09 CN CN201710320025.3A patent/CN107195483B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103427073A (en) * | 2013-08-05 | 2013-12-04 | 同济大学 | Preparation method of mesoporous Si/C composite microsphere as lithium battery negative electrode material |
| CN105217601A (en) * | 2015-11-05 | 2016-01-06 | 北京工业大学 | A kind of preparation method with the porous hollow carbon ball of high-specific surface area |
| 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 |
| CN105752966A (en) * | 2016-01-27 | 2016-07-13 | 同济大学 | Preparation method of graphene/hollow carbon nanometer balls |
| CN105819422A (en) * | 2016-03-17 | 2016-08-03 | 南京理工大学 | Preparation method of nitrogen doped hollow mesoporous carbon sphere |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108232167A (en) * | 2018-01-19 | 2018-06-29 | 洛阳理工学院 | A kind of carbon@ferrosilites hollow-core construction compound and preparation method thereof |
| CN108232167B (en) * | 2018-01-19 | 2020-06-09 | 洛阳理工学院 | Carbon @ iron silicate hollow structure compound and preparation method thereof |
| 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 |
| CN109985643A (en) * | 2019-03-19 | 2019-07-09 | 贵州大学 | A kind of add in-place bromine preparation small size PdKBrThe method of@HSC |
| CN111377431A (en) * | 2020-03-19 | 2020-07-07 | 上海交通大学 | Morphology-controllable-adjustable nitrogen-loaded carbon nanocapsule and preparation method and application thereof |
| CN113096966A (en) * | 2021-04-16 | 2021-07-09 | 广德天运新技术股份有限公司 | High-specific-capacity supercapacitor electrode material based on silicon dioxide and preparation method thereof |
| CN114583140A (en) * | 2022-05-05 | 2022-06-03 | 潍坊科技学院 | Nickel disulfide/silicon composite material with core-shell structure and preparation method and application thereof |
| CN114583140B (en) * | 2022-05-05 | 2022-06-28 | 潍坊科技学院 | Nickel disulfide/silicon composite material with core-shell structure and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107195483B (en) | 2018-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107195483B (en) | A kind of preparation method of the NiO/ Nano carbon balls with nucleocapsid | |
| CN105107540B (en) | Nitrogen-doped carbon nanotube nickel-iron coated oxygen evolution catalytic material for water electrolysis and application | |
| CN104923204A (en) | Preparation method for graphene-coated metal nanometer particle catalyst and application of graphene-coated metal nanometer particle catalyst | |
| CN107051568A (en) | One kind analysis oxygen Fe two cobaltous selenide@N CT composite catalysts of doping and its preparation method and application | |
| CN107176598A (en) | A kind of N doping mesoporous carbon-loaded cobalt-oxidation cobalt nanocomposites and its preparation method and application | |
| CN103318978B (en) | Preparation method of mesoporous nickel cobaltate fiber and application thereof | |
| CN105489389A (en) | Carbon/nickel-cobalt layered double hydroxide composite material and preparation method and application thereof | |
| CN105271203A (en) | Porous co-doped graphene and preparation method thereof | |
| CN104176783B (en) | The preparations and applicatio method of the coated manganese dioxide nanowire of a kind of nitrogen carbon material | |
| CN109546162A (en) | A kind of recyclable preparation method of microporous iron-nitrogen-doped carbon catalyst material | |
| CN105702484B (en) | A kind of preparation method of the mesoporous Nano carbon balls of electrode material for super capacitor NiO/ | |
| CN107128899A (en) | A kind of preparation method of spherical nitrogen-doped carbon nano material | |
| CN103647072B (en) | A kind of nickel oxide surfaces carbon/nitrogen content is than the preparation method of adjustable nitrogen-doped carbon integument | |
| CN110681409A (en) | Carbon tube supported ultra-small VN hydrogen production electrocatalyst, synthesis method and application | |
| CN109243862A (en) | A kind of carbon hollow ball compound of dual modification and its preparation method and application | |
| CN104987715A (en) | Three-dimensional graphene, polyaniline and cobaltosic oxide composite material and preparation method and application | |
| CN108439370A (en) | A kind of preparation method and its usage of two dimension porous boron nitrogen codope carbon nanomaterial | |
| Jiang et al. | NiMoO4@ Co3S4 nanorods with core-shell structure for efficient hydrogen evolution reactions in electrocatalysts | |
| CN107572509A (en) | A kind of hollow carbon graphite ball nano material of N doping and preparation method thereof | |
| CN105140494A (en) | Biomimetic synthesis method of Fe3O4/Fe/C nano composite battery electrode material | |
| CN105152160A (en) | Preparation method of nitrogen-doped carbon microspheres | |
| CN110624540A (en) | Novel ruthenium-based self-supporting electro-catalytic material, preparation method thereof and application thereof in electro-catalytic nitrogen reduction for producing ammonia | |
| CN106960730A (en) | A kind of high stability nickel cobalt double-hydroxide electrode material and preparation method thereof | |
| CN110655120B (en) | Preparation method of mesoporous spherical nickel cobaltate nano material | |
| CN105883925B (en) | A kind of mesoporous mangano-manganic oxide and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180914 Termination date: 20210509 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |