CN106992078A - The preparation method of porous carbon/transiton metal binary oxides micro-sphere material - Google Patents
The preparation method of porous carbon/transiton metal binary oxides micro-sphere material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 25
- 239000002184 metal Substances 0.000 title claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title claims abstract description 8
- 239000004005 microsphere Substances 0.000 title claims description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002077 nanosphere Substances 0.000 claims abstract description 30
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008103 glucose Substances 0.000 claims abstract description 16
- 235000011187 glycerol Nutrition 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 14
- 229910005949 NiCo2O4 Inorganic materials 0.000 claims abstract description 13
- 125000005456 glyceride group Chemical group 0.000 claims abstract description 13
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 150000003624 transition metals Chemical class 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
- 239000007772 electrode material Substances 0.000 abstract description 12
- 239000003990 capacitor Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 238000010276 construction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 239000011805 ball Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 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
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 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
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 210000004508 polar body Anatomy 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000002604 ultrasonography 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
- H01G11/84—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
-
- 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
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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
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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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention relates to a kind of preparation method of porous carbon/transiton metal binary oxides nanometer ball material.By glycerine:Isopropanol=1:3~5 volume ratios are mixed, with Ni (NO3)2·6H2O:Co(NO3)2·6H2O:Glycerine=1:2:250 mass ratioes add Ni (NO3)2·6H2O and Co (NO3)2·6H2O, is stirred to pink colour clear solution, by F127:Ni(NO3)2·6H2O=1~20:9 mass ratioes add F127, stirring to white powder is completely dissolved in clear solution, 180 DEG C of hydro-thermal 6h, obtain NiCo glyceride nanospheres, after washing, drying in the tube furnace of air is passed through, 350 DEG C are raised to from room temperature by 0.5~5 DEG C/min heating rate, 2~4h of constant temperature obtains transiton metal binary oxides NiCo2O4Nanosphere, is scattered in 0.05M glucose solutions, 170 DEG C of hydro-thermal 4h, is carbonized in a nitrogen atmosphere after washing, drying and is kept 4~6h, Temperature fall obtains porous carbon/transiton metal binary oxides nanosphere.Present invention process is simple, and gained porous carbon/binary metal oxide nanosphere shows higher specific capacity value and preferable stable circulation service life as electrode material for super capacitor.
Description
Technical field
The present invention relates to a kind of electrode material for super capacitor porous carbon/transiton metal binary oxides nanometer ball material
Preparation method, belongs to the preparing technical field of electrode material for super capacitor.
Background technology
Ultracapacitor, with higher specific capacitance, storable specific capacitance is more than ten times of traditional capacitor;
Compared with battery, with higher specific power, can abrupt release ultrahigh current, with the charging interval is short, charge efficiency is high, circulation
Service life length, memory-less effect and the features such as substantially without safeguarding, it has filled up traditional capacitor and battery this two class storage
Blank between energy element, in mobile communication, information technology, industrial circle, consumer electronics, electric automobile, Aero-Space and state
There is application prospect of crucial importance and wide in terms of anti-science and technology.In ultracapacitor, electrode material is key factor, it
The main performance index of capacitor is determined, therefore Electrode material is to turn into the key for improving performance of the supercapacitor.It is porous
Carbon material shows good cyclical stability as electrode material for electric double layer capacitor, but its specific capacitance is not high.And transition is golden
Belonging to oxide (nickel oxide, manganese oxide etc.) as Faraday pseudo-capacitance device electrode material has higher specific capacitance, but it is circulated
Stability is relatively poor.Porous carbon/transition metal oxide composite, due to having both advantages concurrently, is now subjected to and grinds
The extensive concern for the person of studying carefully." a kind of electrode material for super capacitor carbon coating nickel oxide NiO/C preparation method " (Chinese invention is special
Profit, application number:201310109686.3) nickel acetate, urea and polyvinylpyrrolidone are dissolved in second alcohol and water, enter water-filling
Thermal response, obtains NiO materials, then NiO is dissolved in glucose solution, proceed hydro-thermal reaction, prepares NiO/C electricity
Pole material.Binary metal oxide is further improved compared to single metal oxide, chemical property.This is primarily due to
Another metal ion species are introduced in metal oxide, more metal ions is participated in redox reaction, by abundant
Redox reaction and more electric charges are stored in electrode, so as to improve energy density and power density;And due to
The interaction of two metal ion species so that binary metal oxide has more preferable electrical conductivity, to the electrochemistry of electrode material
Very big improvement result can be played." a kind of preparation methods of the sour nickel carbon nanometer tube composite materials of cobalt " (Chinese invention patent, Shen
Please number:201510411067.9) it is related to a kind of preparation method of the sour nickel of carbon nanotube loaded nano particle cobalt, the cobalt obtained
Sour nickel carbon nanometer tube composite materials be used for electrode of super capacitor when with good stable electrochemical property.But use
The carbon for stating method preparation has that specific capacitance is low, cyclical stability is poor or preparation method is more complicated with metal oxide composite
The shortcomings of.
The content of the invention
It is an object of the invention to disclose a kind of porous carbon/binary transition metal of the electrode material as ultracapacitor
Oxide nano sphere preparation method.The method can form carbon bag binary metal oxide sandwich construction, and sandwich construction can be reduced
There is provided good supporting construction and inner utilization space for ion diffusion path.Its preparation technology is simple, with higher ratio electricity
Hold, the advantages of good stable circulation performance.
It is of the invention by Ni (NO to reach above-mentioned purpose3)2·6H2O and Co (NO3)2·6H2O presses 1 all the time:2 quality point
Number ratio is dispersed in isopropanol and glycerine mixed solution, is formed after pink colour clear solution, is continuously added a small amount of surfactant
F127, surfactant can control ball-type size and pore-size distribution, reduce nanosphere adhesion degree.By metal oxide dispersion
Continue hydro-thermal in glucose solution, glucose prepolymer is wrapped in metal oxide outer layer, can be in metal oxide after carbonization
Outer layer formation one layer of unsetting carbon of black, the porous carbon so obtained/transiton metal binary oxides microballoon provide one compared with
Big electroactive area, and electrons spread approach is shortened, therefore higher specific capacitance can be obtained.
Specific preparation technology is carried out as follows:
By glycerine:Isopropanol=1:3~5 volume ratio is measured, and is well mixed, then with Ni (NO3)2·6H2O:Co
(NO3)2·6H2O:Glycerine=1:2:250 mass ratio measures Ni (NO3)2·6H2O and Co (NO3)2·6H2O, and they are added
Enter wherein, mixing, after stirring to pink colour clear solution, by F127:Ni(NO3)2·6H2O=1~20:9 mass ratio is added
F127, is stirred continuously to white powder and is completely dissolved in clear solution;It is transferred to 180 DEG C of hydro-thermal 6h, gained in 100mL reactor
Product is washed with distilled water and ethanol, and 12h is dried at 80 DEG C and obtains NiCo glyceride nanospheres;By NiCo glyceride nanospheres
It is placed in the tube furnace for being passed through air, be raised to by 0.5~5 DEG C/min heating rate from room temperature and calcined after 350 DEG C and keep 2~
4h, is naturally cooling to room temperature, and gained atrament is transiton metal binary oxides NiCo2O4Nanosphere;By Dyadic transition gold
Belong to oxide NiCo2O4Nanosphere is scattered in 0.05M glucose solutions, then pours into 170 DEG C of hydro-thermal 4h in 100mL reactor,
Make transiton metal binary oxides outer layer covers glucose prepolymer, finally, in a nitrogen atmosphere with 0.5~5 after washing, drying
DEG C/min heating rate is raised to 350 DEG C from room temperature and carbonizes and keep 4~6h, Temperature fall obtains porous carbon/Dyadic transition gold
Belong to oxide nano sphere.
The invention has the advantages that:
1. the present invention is from Ni (NO3)2·6H2O and Co (NO3)2·6H2O forms NiCo as raw material2O4Binary metal oxygen
Compound, compared to single metal oxide, chemical property is further improved.Another gold is introduced in metal oxide
Belong to ion, more metal ions is participated in redox reaction, by abundant redox reaction by more electric charges
It is stored in electrode, so as to improve energy density and power density;And due to the interaction of two metal ion species so that two
First metal oxide has more preferable electrical conductivity, and very big improvement result is played to the chemical property of electrode material.
2. metal oxide nano ball can form sandwich construction in calcination process, it is possible to reduce ion diffusion path, carry
For good supporting construction and inner utilization space.The abundant hole of porous carbon enables to electric charge to rapidly enter, and passes through cladding
Effect can also increase the electric conductivity of metal oxidation.
3. porous carbon prepared by the present invention/transiton metal binary oxides nanosphere is uniform in size, good dispersion, diameter
400~600nm.Its as electrode material for super capacitor, analysis and tests show that, in 1.0Ag-1During lower discharge and recharge, than electricity
Hold and reach 600Fg-1More than, the capability retention after cycle charge-discharge 5000 times shows higher specific capacity more than 90%
Value and preferable service life cycle.
Embodiment:
Embodiment 1
By glycerine:Isopropanol=1:3 volume ratio is measured, and is well mixed, then with Ni (NO3)2·6H2O:Co(NO3)2·
6H2O:Glycerine=1:2:250 mass ratio adds Ni (NO3)2·6H2O and Co (NO3)2·6H2O, is stirred the mixture for pink colour
After clear solution, by F127:Ni(NO3)2·6H2O=1:9 mass ratio adds F127, is stirred continuously completely molten to white powder
In clear solution.Be transferred to 180 DEG C of hydro-thermal 6h in 100mL reactor, products therefrom washed with distilled water and ethanol several times,
12h is dried at 80 DEG C and obtains NiCo glyceride nanospheres.By NiCo glyceride nanospheres in the tube furnace of air is passed through, by 5
DEG C/min heating rate is raised to from room temperature and calcined after 350 DEG C and keep 2h, is finally naturally cooling to room temperature, gained atrament
As transiton metal binary oxides NiCo2O4.By transiton metal binary oxides NiCo2O4It is scattered in 0.05M glucose solutions
In, 170 DEG C of hydro-thermal 4h in 100mL reactor are poured into, transiton metal binary oxides outer layer covers glucose prepolymer is washed
Wash, dry after be raised to 350 DEG C from room temperature with 0.5 DEG C/min heating rate in a nitrogen atmosphere and carbonize and keep 4h, drop naturally
Temperature obtains porous carbon/transiton metal binary oxides nanosphere.
Embodiment 2
By glycerine:Isopropanol=1:4 volume ratio is measured, and is well mixed, then with Ni (NO3)2·6H2O:Co(NO3)2·
6H2O:Glycerine=1:2:250 mass ratio adds Ni (NO3)2·6H2O and Co (NO3)2·6H2O, is stirred the mixture for pink colour
After clear solution, by F127:Ni(NO3)2·6H2O=5:9 mass ratio adds F127, is stirred continuously completely molten to white powder
In clear solution.Be transferred to 180 DEG C of hydro-thermal 6h in 100mL reactor, products therefrom washed with distilled water and ethanol several times,
12h is dried at 80 DEG C and obtains NiCo glyceride nanospheres.NiCo glyceride nanospheres in the tube furnace of air is passed through, by 3 DEG C/
Min heating rate is raised to from room temperature calcines after 350 DEG C and keeps 3h, is finally naturally cooling to room temperature, gained atrament is
For transiton metal binary oxides NiCo2O4.By NiCo2O4It is scattered in 0.05M glucose solutions, pours into 100mL reactor
In 170 DEG C of hydro-thermal 5h, metal oxide outer layer parcel glucose prepolymer, washing dry after in a nitrogen atmosphere with 1 DEG C/min
Heating rate be raised to 350 DEG C from room temperature and carbonize and keep 5h, Temperature fall obtains porous carbon/transiton metal binary oxides and received
Rice ball.
Embodiment 3
By glycerine:Isopropanol=1:5 volume ratio is measured, and is well mixed, then with Ni (NO3)2·6H2O:Co(NO3)2·
6H2O:Glycerine=1:2:250 mass ratio adds Ni (NO3)2·6H2O and Co (NO3)2·6H2O, is stirred the mixture for pink colour
After clear solution, by F127:Ni(NO3)2·6H2O=10:9 mass ratio adds F127, is stirred continuously complete to white powder
It is dissolved in clear solution.180 DEG C of hydro-thermal 6h in 100mL reactor are transferred to, products therefrom is washed several times with distilled water and ethanol,
12h is dried at 80 DEG C and obtains NiCo glyceride nanospheres.NiCo glyceride nanospheres are in the tube furnace of air is passed through, by 1
DEG C/min heating rate is raised to from room temperature and calcined after 350 DEG C and keep 4h, is finally naturally cooling to room temperature, gained atrament
As transiton metal binary oxides NiCo2O4.By NiCo2O4It is scattered in 0.05M glucose solutions, pours into 100mL reaction
170 DEG C of hydro-thermal 4h in kettle, metal oxide outer layer parcel glucose prepolymer, washing dry after in a nitrogen atmosphere with 3 DEG C/
Min heating rate is raised to 350 DEG C from room temperature and carbonizes and keep 6h, and Temperature fall obtains porous carbon/binary transition metal oxidation
Thing nanosphere.
Embodiment 4
By glycerine:Isopropanol=1:5 volume ratio is measured, and is well mixed, then with Ni (NO3)2·6H2O:Co(NO3)2·
6H2O:Glycerine=1:2:250 mass ratio adds Ni (NO3)2·6H2O and Co (NO3)2·6H2O, is stirred the mixture for pink colour
After clear solution, by F127:Ni(NO3)2·6H2O=20:9 mass ratio adds F127, is stirred continuously complete to white powder
It is dissolved in clear solution.180 DEG C of hydro-thermal 6h in 100mL reactor are transferred to, products therefrom is washed several times with distilled water and ethanol,
12h is dried at 80 DEG C and obtains NiCo glyceride nanospheres.NiCo glyceride nanospheres are pressed in the tube furnace of air is passed through
0.5 DEG C/min heating rate is raised to from room temperature calcines after 350 DEG C and keeps 4h, is finally naturally cooling to room temperature, gained black
Material is transiton metal binary oxides NiCo2O4.By NiCo2O4It is scattered in 0.05M glucose solutions, pours into 100mL's
170 DEG C of hydro-thermal 4h in reactor, metal oxide outer layer parcel glucose prepolymer, in a nitrogen atmosphere with 5 after washing is dry
DEG C/min heating rate is raised to 350 DEG C from room temperature and carbonizes and keep 6h, Temperature fall obtains porous carbon/binary transition metal oxygen
Compound nanosphere.
Analysis test result shows that the porous carbon that embodiment 1-4 is obtained/transiton metal binary oxides nanosphere size is equal
It is even, a diameter of 400~600nm, the sample that embodiment 1-4 is obtained and electrically conductive graphite, binding agent (PTFE) in mass ratio 8:1:1
Mixing, adds ethanol as dispersant and ultrasound 30min formation slurries.The slurry is placed in 60 DEG C of baking oven volatilization ethanol,
Thin slice is pressed into when slurry is converted into leather hard, it is about 1cm or so then to intercept diameter on thin slice with card punch
Circular electric pole piece, and be placed on 90~100 DEG C of 12~24h of drying to after constant weight, urged it against using high hydraulic pressure tablet press machine
Electrode of super capacitor is made in nickel foam, electrochemical property test can be carried out after soaking 24h in the electrolytic solution.Using three electricity
Polar body system, using porous carbon/transiton metal binary oxides nanosphere as working electrode, saturated calomel electrode is reference electrode, bubble
Foam nickel electrode is that, to electrode, the 6M KOH aqueous solution is electrolyte.In the case where potential window is 0~0.5V, the ratio of above-mentioned sample is tested
Electric capacity, current density is 1Ag-1, its its specific capacitance surveyed is 600~800Fg-1After current potential, cycle charge-discharge 5000 times,
Its capability retention is 90~94%, shows higher specific capacity and preferable service life cycle.
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 porous carbon/transiton metal binary oxides micro-sphere material, it is characterised in that:
First glycerine is measured by volume:Isopropanol=1:3~5, it is well mixed, then with Ni (NO3)2·6H2O:Co(NO3)2·
6H2O:Glycerine=1:2:250 mass ratio measures Ni (NO3)2·6H2O and Co (NO3)2·6H2O, and add them into wherein,
Mixing, after stirring to pink colour clear solution, by F127:Ni(NO3)2·6H2O=1~20:9 mass ratio adds F127, constantly
Stirring to white powder is completely dissolved in clear solution;180 DEG C of hydro-thermal 6h in 100mL reactor are transferred to, products therefrom steams
Distilled water and ethanol washing, dry 12h obtains NiCo glyceride nanospheres at 80 DEG C;NiCo glyceride nanospheres are placed in and are passed through
In the tube furnace of air, it is raised to by 0.5~5 DEG C/min heating rate from room temperature and is calcined after 350 DEG C and keep 2~4h, it is natural
Room temperature is cooled to, gained atrament is transiton metal binary oxides NiCo2O4Nanosphere;Binary transition metal is aoxidized
Thing NiCo2O4Nanosphere is scattered in 0.05M glucose solutions, then pours into 170 DEG C of hydro-thermal 4h in 100mL reactor, binary mistake
Metal oxide outer layer parcel glucose prepolymer is crossed, finally, in a nitrogen atmosphere with 0.5~5 DEG C/min's after washing, drying
Heating rate is raised to 350 DEG C of charings from room temperature and keeps 4~6h, and Temperature fall obtains porous carbon/transiton metal binary oxides
Nanosphere;
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;
Above raw material is commercially available technical grade product.
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