CN106328383A - Preparation method of nickel cobalt oxide nanorod composite material wrapped by carbon having microspheric grading structure - Google Patents
Preparation method of nickel cobalt oxide nanorod composite material wrapped by carbon having microspheric grading structure Download PDFInfo
- Publication number
- CN106328383A CN106328383A CN201610817981.8A CN201610817981A CN106328383A CN 106328383 A CN106328383 A CN 106328383A CN 201610817981 A CN201610817981 A CN 201610817981A CN 106328383 A CN106328383 A CN 106328383A
- Authority
- CN
- China
- Prior art keywords
- nickel
- preparation
- cobalt acid
- composite material
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 title abstract 5
- 239000002073 nanorod Substances 0.000 title abstract 4
- 239000004005 microsphere Substances 0.000 title abstract 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 13
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 13
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims abstract description 11
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 92
- 229910052759 nickel Inorganic materials 0.000 claims description 46
- 239000002253 acid Substances 0.000 claims description 44
- 229910017052 cobalt Inorganic materials 0.000 claims description 44
- 239000010941 cobalt Substances 0.000 claims description 44
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 44
- 229940097267 cobaltous chloride Drugs 0.000 claims description 12
- 229920006391 phthalonitrile polymer Polymers 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 235000013877 carbamide Nutrition 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- -1 dimethoxy nitrile Chemical class 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 239000007772 electrode material Substances 0.000 abstract description 12
- 230000004087 circulation Effects 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000010303 mechanochemical reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229910001922 gold oxide Inorganic materials 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000003466 welding 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
- H01G11/22—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
-
- 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
-
- 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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
-
- 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
-
- 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)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of nickel cobalt oxide nanorod composite material wrapped by carbon having a microspheric grading structure. The preparation method comprises steps that mixed solvent of ethylene glycol and water is prepared; nickel chloride, cobalt chloride, urea, and bisphthalonitrile are dispersed; nickel phthalocyanine/ cobalt carbonate composite material is acquired after high temperature crystallization; nickel phthalocyanine/ cobalt carbonate composite material is calcined. The prepared composite material is a powder-shaped amorphous material, and nickel cobalt oxide crystals wrapped by the carbon exist in the form of the nanorod, and are gathered together to form a microspheric grading structure, and are distributed uniformly. By adopting the above mentioned structure, the conductivity of the nickel cobalt oxide is improved, and the stability of the whole material is improved. When the composite material is used as an electrode material of a super capacitor, the stability and the conductivity of the electrode material are greatly improved. The nickel cobalt oxide nanorod composite material is advantageous in that high specific capacity and good circulation stability are provided; the specific capacity reaches 575F/g, and a capacity retention ratio is kept at 95.2%after 3000 times of charging and discharging; an excellent electrochemical performance is provided.
Description
Technical field
The invention belongs to electrode material synthesis field, relate to a kind of microspheroidal hierarchy carbon parcel cobalt acid nanosized nickel rods multiple
The preparation method of condensation material.
Background technology
Under the dual test of scarcity of resources and environmental pollution, explore the continuable energy-storage travelling wave tube of cleaning extremely urgent.Super
Level capacitor, as the electrochemical energy storage element of a kind of excellence, because having high power density, high-energy-density, large current density
The lot of advantages such as electric and good cyclical stability and receive much concern.It is widely used in electronics, automobile, the energy and Aero-Space etc.
Every field.As the important component part of ultracapacitor, electrode material becomes one of study hotspot.
Based at the quick redox reaction of electrode surface, transition metal oxide electrode material has high power density
With advantages such as high theoretical specific capacity, cause the great interest of researcher.Wherein, ruthenium-oxide and gold oxide are the most counterfeit
Capacitance electrode material, but expensive because of it and welding characteristic is difficult to commercial application；And cobalt acid nickel is as a kind of emerging
Transition metal oxide electrode material, has electric conductivity more higher than monometallic transition oxide and more complicated oxidoreduction mistake
Journey, and aboundresources, environmental friendliness, is the ultracapacitor transition metal oxide electrode material of great potential.
The common method preparing cobalt acid nickel has sol-gal process, coprecipitation, mechanochemical reaction etc., wherein sol-gal process
The cobalt acid nickel of preparation can obtain the uniformity of molecular level, and chemical reaction is easily carried out, temperature required relatively low.But it there is also can not
The shortcoming avoided, i.e. cost are high, and the response time is long, it is often necessary to several days even week ages, and the material prepared exists one
A little small holes (such as Chinese patent CN 102092797 B etc.).When coprecipitation prepares cobalt acid nickel with mechanochemical reaction, technique is relative
Simply, the time is short, but it cannot be guaranteed that the homogeneity of material, the effect of the precipitant owing to adding, material there will be reunion or
The uneven phenomenon of component (such as Chinese patent CN 104659358 A, CN 103318978 B etc.).And solvent-thermal method is the most permissible
Ensure the homogeneity of material, also save the preparation time of material (such as Chinese patent CN 104291385 B, CN 105399150
A etc.), it is the good method of one preparing cobalt acid nickel.But, compared to traditional material with carbon element, simple cobalt acid nickel electrode material is still
So there is the defects such as poorly conductive, cyclical stability difference.
Summary of the invention
It is an object of the invention to: the problem existed for prior art, it is provided that a kind of microspheroidal hierarchy carbon parcel
The preparation method of cobalt acid nanosized nickel rods composite, prepares the composite of novel cobalt acid nickel and material with carbon element, improves it and lead
Electrically and cyclical stability, its chemical property is improved.
To achieve these goals, the technical solution used in the present invention is:
The preparation method of a kind of microspheroidal hierarchy carbon parcel cobalt acid nanosized nickel rods composite, comprises the following steps:
(1) ethylene glycol and water are mixed with the volume ratio of 1-3:1, prepare mixed solvent；
(2) weighing Nickel dichloride., cobaltous chloride, carbamide and bi-phthalonitrile, to be dispersed in mixing prepared by step (1) molten
In agent, form mixed solution；Wherein, the mol ratio of Nickel dichloride., cobaltous chloride and carbamide is 1:1:10.5, Nickel dichloride., cobaltous chloride and
The mass ratio of bi-phthalonitrile is 1:1:0.2-0.45；
(3) mixed solution prepared by step (2) is poured in crystallizing kettle inner bag, crystallization 3-8 hour at 150-200 DEG C；
(4) treat that crystallizing kettle is down to room temperature, successively sucking filtration, clean, dry, obtain Nickel Phthalocyanine/cobalt carbonate composite；
(5) Nickel Phthalocyanine/cobalt carbonate composite prepared by step (4) under air atmosphere 400 DEG C calcine 3 hours, obtain micro-
Spherical hierarchy carbon parcel cobalt acid nanosized nickel rods composite.
As the preferred version of the present invention, in described step (1), the volume ratio of ethylene glycol and water is 1.5-2:1.
As the preferred version of the present invention, in described step (2), Nickel dichloride., cobaltous chloride, carbamide and bi-phthalonitrile are equal
Even it is scattered in mixed solvent prepared by step (1), ultrasonic disperse 1 hour.
As the preferred version of the present invention, in described step (2), the quality of Nickel dichloride., cobaltous chloride and bi-phthalonitrile
Ratio is 1:1:0.3-0.35.
As the preferred version of the present invention, in described step (3), crystallization temperature is 200 DEG C, and crystallization time is 5 hours.
The beneficial effects of the present invention is:
1, composite prepared by the present invention is powder amorphous material, its pattern be carbon parcel cobalt acid nickel crystal with
Nanometer rods form exists, and is gathered into microspheroidal hierarchy and is uniformly distributed；This structure not only increases the electric conductivity of cobalt acid nickel,
Also improve the stability that material is overall；During as the electrode material of ultracapacitor, substantially increase electrode material
Stability and electric conductivity, possess the advantage such as height ratio capacity, good circulation stability, and specific capacity is up to 575F/g, 3000 charge and discharges
Capacitance conservation rate, still 95.2%, has the chemical property of excellence.
2, the present invention uses the mixed solution of water and ethylene glycol to be solvent, provides pyroreaction ring for bi-phthalonitrile
Border so that it is reaction generates phthalocyanine；Phthalocyanine is the plane macrocyclic compound with four indole rings, easily resolves into through low-temperature carbonization
There is the material with carbon element of planar structure；The present invention is that fake capacitance electrode material transition metal oxide provides a kind of new composite carbon
Source phthalocyanine, a kind of conductive organic matter with rock-steady structure and performance.
Accompanying drawing explanation
Fig. 1 is that the microspheroidal hierarchy carbon parcel cobalt acid nanosized nickel rods composite of embodiment 1 preparation is in (a) low amplification
SEM figure under multiple and (b) high-amplification-factor；
Fig. 2 is (a) Nickel Phthalocyanine/cobalt carbonate composite and the XRD of (b) carbon parcel cobalt acid nickel composite material in embodiment 1
Figure；
Fig. 3 be in embodiment 1 carbon parcel cobalt acid nickel electrode 10,50, CV figure under 100mv/s scanning speed；
Fig. 4 be in embodiment 1 carbon parcel cobalt acid nickel electrode 0.5,1, crossing current charge and discharge electrograph under 2A/g electric current density；
Fig. 5 is the circulation figure of carbon parcel cobalt acid nickel electrode in embodiment 1；
Fig. 6 be in embodiment 2 carbon parcel cobalt acid nickel electrode 10,50, CV figure under 100mv/s scanning speed；
Fig. 7 be in embodiment 2 carbon parcel cobalt acid nickel electrode 0.5,1, crossing current charge and discharge electrograph under 2A/g electric current density.
Detailed description of the invention
In order to make the object, technical solutions and advantages of the present invention clearer, below in conjunction with excellent to the present invention of accompanying drawing
Embodiment is selected to be described in detail.
Embodiment 1
The preparation method of a kind of microspheroidal hierarchy carbon parcel cobalt acid nanosized nickel rods composite, comprises the following steps:
(1) ethylene glycol and water are mixed with the volume ratio of 1.5:1, prepare mixed solvent；
(2) weigh 0.375g Nickel dichloride., 0.375g cobaltous chloride, 1.985g carbamide and 0.125g bi-phthalonitrile uniformly to divide
Dissipate in 50ml mixed solvent prepared by step (1), ultrasonic disperse 1 hour, form mixed solution；
(3) mixed solution prepared by step (2) is poured in crystallizing kettle inner bag, crystallization 5 hours at 200 DEG C；
(4) treat that crystallizing kettle is down to room temperature, successively sucking filtration, clean, dry, obtain Nickel Phthalocyanine/cobalt carbonate composite；
(5) Nickel Phthalocyanine/cobalt carbonate composite prepared by step (4) under air atmosphere 400 DEG C calcine 3 hours, obtain micro-
Spherical hierarchy carbon parcel cobalt acid nanosized nickel rods composite.
The composition of the microspheroidal hierarchy carbon parcel cobalt acid nanosized nickel rods composite of embodiment 1 preparation and pattern such as figure
Shown in 1 and 2, its pattern is that the cobalt acid nickel crystal of carbon parcel exists with nanometer rods form, and it is equal to be gathered into microspheroidal hierarchy
Even distribution.
The preparation of carbon parcel cobalt acid nickel electrode: microspheroidal hierarchy carbon parcel cobalt acid nickel nanometer prepared by embodiment 1
Rod composite material, acetylene black and aqueous binders 80:10:10 in mass ratio mixes, and sizes mixing, and is coated uniformly in nickel foam,
Electrode slice is put in vacuum drying oven, at 70 DEG C, be dried 6h.Afterwards with powder compressing machine 10MPa tabletting, at three electrode systems
System is lower tests its chemical property.With saturated calomel electrode as reference electrode, platinum electrode is to electrode, and 3M KOH is electrolyte,
In occasion China electrochemical workstation, carbon parcel cobalt acid nickel electrode is circulated volt-ampere and crossing current charge-discharge performance test.
Fig. 3 be in embodiment 1 carbon parcel cobalt acid nickel electrode 10,50, CV figure under 100mv/s scanning speed, from figure
It can be seen that the suitable voltage range of this sample is 0-0.5V, and during 100mV/s, the deformation of CV figure is the least, is suitable for large current density
Electricity.
Fig. 4 be in embodiment 1 carbon parcel cobalt acid nickel electrode 0.5,1, crossing current charge and discharge electrograph under 2A/g electric current density,
When electric current density is 0.5A/g, specific capacity reaches 575F/g.
Fig. 5 is the circulation figure of carbon parcel cobalt acid nickel electrode in embodiment 1, and as seen from the figure, after 3000 circulations, capacity is protected
Holdup still has 95.2%.
Embodiment 2
The preparation method of a kind of microspheroidal hierarchy carbon parcel cobalt acid nanosized nickel rods composite, comprises the following steps:
(1) ethylene glycol and water are mixed with the volume ratio of 1.5:1, prepare mixed solvent；
(2) weigh 0.375g Nickel dichloride., 0.375g cobaltous chloride, 1.985g carbamide and 0.125g bi-phthalonitrile uniformly to divide
Dissipate in 50ml mixed solvent prepared by step (1), ultrasonic disperse 1 hour, form mixed solution；
(3) mixed solution prepared by step (2) is poured in crystallizing kettle inner bag, crystallization 8 hours at 180 DEG C；
(4) treat that crystallizing kettle is down to room temperature, successively sucking filtration, clean, dry, obtain Nickel Phthalocyanine/cobalt carbonate composite；
(5) Nickel Phthalocyanine/cobalt carbonate composite prepared by step (4) under air atmosphere 400 DEG C calcine 3 hours, obtain micro-
Spherical hierarchy carbon parcel cobalt acid nanosized nickel rods composite.
The preparation of carbon parcel cobalt acid nickel electrode: microspheroidal hierarchy carbon parcel cobalt acid nickel nanometer prepared by embodiment 2
Rod composite material, acetylene black and aqueous binders 80:10:10 in mass ratio mixes, and sizes mixing, and is coated uniformly in nickel foam,
Electrode slice is put in vacuum drying oven, at 70 DEG C, be dried 6h.Afterwards with powder compressing machine 10MPa tabletting, at three electrode systems
System is lower tests its chemical property.With saturated calomel electrode as reference electrode, platinum electrode is to electrode, and 3M KOH is electrolyte,
In occasion China electrochemical workstation, carbon parcel cobalt acid nickel electrode is circulated volt-ampere and crossing current charge-discharge performance test.
Fig. 6 be in embodiment 2 carbon parcel cobalt acid nickel electrode 10,50, CV figure under 100mv/s scanning speed, from figure
It can be seen that the suitable voltage range of this sample is 0-0.5V, but during 100mV/s, CV figure deformation ratio is more apparent shows that it is big
Current charge-discharge electrical property relatively embodiment 1 material is poor.
Fig. 7 be in embodiment 2 carbon parcel cobalt acid nickel electrode 0.5,1, crossing current charge and discharge electrograph under 2A/g electric current density,
When electric current density is 0.5A/g, specific capacity reaches 520F/g.
Finally illustrating, above example is only in order to illustrate technical scheme and unrestricted, although by ginseng
According to the preferred embodiments of the present invention, invention has been described, it should be appreciated by those of ordinary skill in the art that can
In the form and details it is made various change, the present invention limited without departing from appended claims
Spirit and scope.
Claims (5)
1. the preparation method of a microspheroidal hierarchy carbon parcel cobalt acid nanosized nickel rods composite, it is characterised in that: include
Following steps:
(1) ethylene glycol and water are mixed with the volume ratio of 1-3:1, prepare mixed solvent；
(2) weigh Nickel dichloride., cobaltous chloride, carbamide and bi-phthalonitrile to be dispersed in mixed solvent prepared by step (1),
Form mixed solution；Wherein, the mol ratio of Nickel dichloride., cobaltous chloride and carbamide is 1:1:10.5, Nickel dichloride., cobaltous chloride and double adjacent benzene
The mass ratio of dimethoxy nitrile is 1:1:0.2-0.45；
(3) mixed solution prepared by step (2) is poured in crystallizing kettle inner bag, crystallization 3-8 hour at 150-200 DEG C；
(4) treat that crystallizing kettle is down to room temperature, successively sucking filtration, clean, dry, obtain Nickel Phthalocyanine/cobalt carbonate composite；
(5) Nickel Phthalocyanine/cobalt carbonate composite prepared by step (4) under air atmosphere 400 DEG C calcine 3 hours, obtain microspheroidal
Hierarchy carbon parcel cobalt acid nanosized nickel rods composite.
The preparation method of microspheroidal hierarchy carbon the most according to claim 1 parcel cobalt acid nanosized nickel rods composite,
It is characterized in that: in described step (1), the volume ratio of ethylene glycol and water is 1.5-2:1.
The preparation method of microspheroidal hierarchy carbon the most according to claim 1 parcel cobalt acid nanosized nickel rods composite,
It is characterized in that: in described step (2), Nickel dichloride., cobaltous chloride, carbamide and bi-phthalonitrile are dispersed in step (1) system
In standby mixed solvent, ultrasonic disperse 1 hour.
The preparation method of microspheroidal hierarchy carbon the most according to claim 1 parcel cobalt acid nanosized nickel rods composite,
It is characterized in that: in described step (2), the mass ratio of Nickel dichloride., cobaltous chloride and bi-phthalonitrile is 1:1:0.3-0.35.
The preparation method of microspheroidal hierarchy carbon the most according to claim 1 parcel cobalt acid nanosized nickel rods composite,
It is characterized in that: in described step (3), crystallization temperature is 200 DEG C, and crystallization time is 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610817981.8A CN106328383B (en) | 2016-09-12 | 2016-09-12 | A kind of preparation method of microspheroidal hierarchy carbon parcel cobalt acid nanosized nickel rods composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610817981.8A CN106328383B (en) | 2016-09-12 | 2016-09-12 | A kind of preparation method of microspheroidal hierarchy carbon parcel cobalt acid nanosized nickel rods composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106328383A true CN106328383A (en) | 2017-01-11 |
| CN106328383B CN106328383B (en) | 2018-05-11 |
Family
ID=57787671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610817981.8A Active CN106328383B (en) | 2016-09-12 | 2016-09-12 | A kind of preparation method of microspheroidal hierarchy carbon parcel cobalt acid nanosized nickel rods composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106328383B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107697891A (en) * | 2017-09-30 | 2018-02-16 | 合肥师范学院 | The preparation method of carbon parcel core shell structure bismuth telluride nanometer rods and its carbon parcel core shell structure bismuth telluride nanometer rods of preparation and application |
| CN110010360A (en) * | 2019-04-09 | 2019-07-12 | 西北大学 | A kind of closely spherical nickel molybdate/Asia phthalocyanine composite material and its preparation method and application |
| CN110212204A (en) * | 2019-04-22 | 2019-09-06 | 浙江大学 | A kind of efficient carbon nanosheet support type fuel cell positive electrode and its preparation method and application |
| CN113912924A (en) * | 2021-11-05 | 2022-01-11 | 杭州老板电器股份有限公司 | Composite noise reduction material, preparation method thereof, equipment shell and equipment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399151A (en) * | 2015-11-24 | 2016-03-16 | 青岛能迅新能源科技有限公司 | Preparation method of NiCo2O4 nano-material |
| CN105399150A (en) * | 2015-11-24 | 2016-03-16 | 青岛能迅新能源科技有限公司 | NiCo2O4 nano-material as well as preparation method and application thereof |
| CN105826551A (en) * | 2016-05-19 | 2016-08-03 | 青岛大学 | Preparation method of dumbbell type NiCo2O4 lithium ion battery anode material |
-
2016
- 2016-09-12 CN CN201610817981.8A patent/CN106328383B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399151A (en) * | 2015-11-24 | 2016-03-16 | 青岛能迅新能源科技有限公司 | Preparation method of NiCo2O4 nano-material |
| CN105399150A (en) * | 2015-11-24 | 2016-03-16 | 青岛能迅新能源科技有限公司 | NiCo2O4 nano-material as well as preparation method and application thereof |
| CN105826551A (en) * | 2016-05-19 | 2016-08-03 | 青岛大学 | Preparation method of dumbbell type NiCo2O4 lithium ion battery anode material |
Non-Patent Citations (8)
| Title |
|---|
| BING SUN 等: "Hierarchical NiCo2O4 nanorods as an efficient cathode catalyst for rechargeable non-aqueous Li–O2 batteries", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
| EFAT JOKAR 等: "Synthesis and characterization of NiCo2O4 nanorods for preparation of supercapacitor electrodes", 《JOURNAL OF SOLID STATE ELECTROCHEMISTRY》 * |
| GENQIANG ZHANG 等: "Controlled growth of NiCo₂O₄ nanorods and ultrathin nanosheets on carbon nanofibers for high-performance supercapacitors", 《SCIENTIFIC REPORTS》 * |
| JUN LIU 等: "Facile synthesis of NiCo2O4 nanorod arrays on Cu conductive substrates as superior anode materials for high-rate Li-ion batteries", 《CRYSTENGCOMM》 * |
| 刘大军 等: "《有机化学实验》", 31 August 2014, 清华大学出版社 * |
| 安翠华: "NiCo2O4材料微纳结构的构筑及电化学性能研究", 《万方学位论文库》 * |
| 徐蓓: "金属酞菁对锂离子电池正极材料LiFePO4的改性及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 颜朝国: "《大学化学实验·综合与探索性实验》", 30 September 2006, 南京大学出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107697891A (en) * | 2017-09-30 | 2018-02-16 | 合肥师范学院 | The preparation method of carbon parcel core shell structure bismuth telluride nanometer rods and its carbon parcel core shell structure bismuth telluride nanometer rods of preparation and application |
| CN110010360A (en) * | 2019-04-09 | 2019-07-12 | 西北大学 | A kind of closely spherical nickel molybdate/Asia phthalocyanine composite material and its preparation method and application |
| CN110010360B (en) * | 2019-04-09 | 2021-01-05 | 西北大学 | Near-spherical nickel molybdate/subphthalocyanine composite material and preparation method and application thereof |
| CN110212204A (en) * | 2019-04-22 | 2019-09-06 | 浙江大学 | A kind of efficient carbon nanosheet support type fuel cell positive electrode and its preparation method and application |
| CN113912924A (en) * | 2021-11-05 | 2022-01-11 | 杭州老板电器股份有限公司 | Composite noise reduction material, preparation method thereof, equipment shell and equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106328383B (en) | 2018-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Defective N/S‐codoped 3D cheese‐like porous carbon nanomaterial toward efficient oxygen reduction and Zn–air batteries | |
| CN107221641B (en) | A kind of lignin is the MoS of carbon source2The preparation method of@C combination electrode material | |
| Wang et al. | Morphology evolution of urchin-like NiCo 2 O 4 nanostructures and their applications as psuedocapacitors and photoelectrochemical cells | |
| CN103824702B (en) | The preparation method of Crusta Penaeus seu Panulirus Quito pore carbon electrode material of nitrogen/phosphor codoping | |
| CN106328383A (en) | Preparation method of nickel cobalt oxide nanorod composite material wrapped by carbon having microspheric grading structure | |
| CN103440998B (en) | A kind of cobalt acid zinc nanometer sheet array/nickel foam combination electrode, preparation method and application thereof | |
| CN102709058B (en) | Method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors | |
| CN104681823A (en) | Nitrogen-doped graphene and Co3O4 hollow nanosphere composite material as well as preparation method and application of composite material | |
| CN109908938A (en) | A kind of preparation method of Novel electrolytic water Oxygen anodic evolution catalyst Co@NC/CNT | |
| CN107188171B (en) | Porous carbon materials and preparation method and the porous carbon-based electrode material for supercapacitor prepared using the porous carbon materials | |
| CN108940285A (en) | A kind of preparation method and application of flexibility electrolysis water catalysis material | |
| CN106960948A (en) | A kind of MoSx/ carbon black nano composite material, its preparation method and its application | |
| Liao et al. | Electrochemical performance of metal-organic framework synthesized by a solvothermal method for supercapacitors | |
| CN108962616A (en) | A kind of CoS/CoNi (OH)4Porous nano composite material and preparation method | |
| CN102516764B (en) | Polyaniline nanowire/ graded porous carbon composite material as well as preparation method and application thereof | |
| CN106898496B (en) | The preparation method and application of bullet-shaped cobalt phosphate nickel ammonium particle with multilayer scale | |
| Cao et al. | Hierarchical core/shell structures of ZnO nanorod@ CoMoO 4 nanoplates used as a high-performance electrode for supercapacitors | |
| CN105152160A (en) | Preparation method of nitrogen-doped carbon microspheres | |
| CN106206082A (en) | There is the preparation method and application of the nickel oxide/graphene combination electrode of electrochemical capacitance energy storage characteristic | |
| Tian et al. | Dual modification of BiVO4 photoanode by rare earth element neodymium doping and further NiFe2O4 co-catalyst deposition for efficient photoelectrochemical water oxidation | |
| CN107946089A (en) | A kind of MnFe2O4The preparation method of/rGO composite materials and its application as electrode material for super capacitor | |
| CN105826077A (en) | Composite pair electrode used in quantum-dot sensitized solar cell and preparation method for same | |
| CN106409528B (en) | A kind of ZnFe2O4Nano particle/Carbon fibe hybrid supercapacitor electrode material and preparation method thereof | |
| CN105355461B (en) | One kind is based on MoS2Asymmetric Supercapacitor of anode and preparation method thereof | |
| CN102874884A (en) | Preparation method of super capacitor electrode material (nickel oxide) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |