CN105551818A - Beta-cobalt nickel hydroxide and nickel plated carbon nanotube composite material and preparation method and application thereof - Google Patents
Beta-cobalt nickel hydroxide and nickel plated carbon nanotube composite material and preparation method and application thereof Download PDFInfo
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- CN105551818A CN105551818A CN201610036643.0A CN201610036643A CN105551818A CN 105551818 A CN105551818 A CN 105551818A CN 201610036643 A CN201610036643 A CN 201610036643A CN 105551818 A CN105551818 A CN 105551818A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 89
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007772 electrode material Substances 0.000 claims abstract description 12
- 238000007747 plating Methods 0.000 claims description 75
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 48
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 239000002073 nanorod Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 15
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 5
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 8
- 239000011149 active material Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229910000314 transition metal oxide Inorganic materials 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 238000006479 redox reaction Methods 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 239000002060 nanoflake Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910002640 NiOOH Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 206010068052 Mosaicism Diseases 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- MXEHMOBFYMIGAE-UHFFFAOYSA-L cobalt(2+);nickel;dihydroxide Chemical compound [OH-].[OH-].[Co+2].[Ni] MXEHMOBFYMIGAE-UHFFFAOYSA-L 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 210000003765 sex chromosome Anatomy 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910003160 β-NiOOH Inorganic materials 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
- H01G11/30—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
- H01G11/10—Multiple hybrid or EDL capacitors, e.g. arrays or modules
- H01G11/12—Stacked hybrid or EDL capacitors
-
- 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
- H01G11/84—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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of nano functional materials and particularly relates to a beta-cobalt nickel hydroxide and nickel plated carbon nanotube composite material and a preparation method and an application thereof. According to the preparation method, a nickel plated carbon nanotube is selected and used as a growth template of beta-cobalt nickel hydroxide, and cobalt ions are doped in lamellar rodlike materials of beta-nickel hydroxide and the nickel plated carbon nanotube through a three-step solvothermal reaction and hydro-thermal treatment to obtain a composite material with a three-dimensional multi-stage structure. A flower-shaped nanosheet of beta-cobalt nickel hydroxide vertically grows on the surface of the nickel plated carbon nanotube. The beta-cobalt nickel hydroxide and nickel plated carbon nanotube composite material serving as an electrode material of a supercapacitor has high specific capacity, the specific capacity of the material reaches up to 1,982Fg<-1> under the current density of 1Ag<-1>, and the capacity retention ratio after circulation for 1,000 circles under the current is 86.8%. In addition, the nano material is low in preparation cost, high in efficiency and easier to industrially expand for solving the problem in actual application, and the material serving as a novel electrode material capable of being widely applied to the supercapacitor has a wide application prospect.
Description
Technical field
The invention belongs to nano-functional material technical field, be specifically related to a kind of β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material and preparation method thereof, and the application in ultracapacitor.
Background technology
A lot of transition metal oxide/hydroxide is considered to ideal fake capacitance material because they there is active, the very high theoretical capacity of good electrochemical reaction, aboundresources, cost are lower, may there is polyelectron reaction simultaneously
[1-2].Compared with double electric layer capacitor, the energy density of fake capacitance capacitor is higher, because Reversible redox reaction fast can occur fake capacitance material, the Capacity Ratio electric double layer capacitance contributed is high doubly a lot.This Reversible redox reaction fast usually occurs in the surface of active material or nearly surf zone, especially under fast charging and discharging condition
[3-4].In order to can active material be made full use of, reach higher ultracapacitor performance, usually by the topographic design formation of nanostructured of active material or loose structure, because can effectively shorten ion diffuse distance like this, more ion diffuse path will be provided.This can not only improve the utilance of active material, can accelerate the speed of Reversible redox reaction simultaneously, shortens the discharge and recharge time, and improve power output, this is highly beneficial to the performance of ultracapacitor.The pattern met this requirement is very many, the nickel hydroxide of such as nano-sheet
[5-8], the nickel hydroxide of nano strip
[9], the nickel oxide of nano strip
[10-12], the nickel hydroxide of multilevel hierarchy
[13-15], the nickel oxide of loose structure
[16-18].
Although these topographic design shorten ion diffuse distance greatly, add ion diffuse path, but the low electric conductivity of transition metal oxide/hydroxide has had a strong impact on the transmission of electronics, hinder the carrying out of redox reaction, finally cause the specific capacity of electrode material not high, high rate performance is poor.The most effective method of current raising electrode material conductivity is that transition metal oxide/hydroxide and conductive material are carried out compound.Conventional electric conducting material comprises material with carbon element
[19-27], conducting polymer
[28-29], electro-conductive glass
[30], metal collector
[31-38]deng.Wherein, material with carbon element is the most frequently used, kind is also very many, such as Graphene, carbon nano-tube, carbon fiber, active carbon, carbon aerogels etc., because they have good electrochemical stability, very high specific area, extraordinary conductivity and very high mechanical strength etc.
[39-40].
But, directly carry out the growth fraction of transition metal oxide/hydroxide at carbon material surface more difficult, because their compatibility is poor.In order to improve receptive surface sex chromosome mosaicism, usually all need to carry out finishing or modification to material with carbon element.Wherein the most frequently used method is oxidation processes, introduces oxygen-containing functional group at carbon material surface, promotes that transition metal oxide/hydroxide is in the growth of carbon material surface.But oxidation processes can damage the structure of material with carbon element, causes the reduction of its conductivity, simultaneous oxidation process is a more loaded down with trivial details process, and degree of oxidation is not easy to control
[41].For electro-conductive glass and metal collector, just there is not this problem, because the compatibility of the metallic atom on their surfaces and oxygen atom and transition metal oxide/hydroxide is very good, the growth of transition metal oxide/hydroxide on its surface can be realized very easily.But the density of electro-conductive glass and metal collector is very high, the load capacity of active material is very limited simultaneously: their specific area is very limited on the one hand; On the other hand, active material is limited at the growth thickness on their surfaces, generally within several microns.This just causes the capacity of electrode not high, limits its application in ultracapacitor.
The present invention selects nickel-plating carbon nanotube (Ni-CNTs) as the growth templates of β-nickel hydroxide.By two step solvent heat treatment, the β-nickel hydroxide and nickel-plating carbon nanotube composite material that have ZnO thin film are successfully prepared.β-cobalt hydroxide nickel flower-like nanometer thin slice vertical-growth, on nickel-plating carbon nanotube surface, forms the nanometer rods with three-dimensional multistage structure.This composite material, as electrode material for super capacitor, shows very high specific capacity and good cycle performance.
Summary of the invention
The object of the present invention is to provide that specific capacity is high, good cycle, the composite material with three-dimensional multistage structure with low cost, and the preparation method and application of this material are provided.
The composite material of three-dimensional multistage structure provided by the invention, for β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material, the growth templates of this composite material using nickel-plating carbon nanotube as β-nickel hydroxide, β-nickel hydroxide flower-like nanometer thin slice the vertical-growth of ZnO thin film, on nickel-plating carbon nanotube surface, forms the coated of densification.
The present invention also provides the preparation method of β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material, and concrete steps are:
(1) solvent-thermal process of alpha-nickel hydroxide and nickel-plating carbon nanotube composite nanorod:
First, supersonic cleaning machine is utilized to add 80 ± 1mg nickel-plating carbon nanotube in the diethylene glycol of 30 ± 1mL, ultrasonic 30 ~ 35min; Then in this suspension-turbid liquid, add Nickel dichloride hexahydrate 285 ± 5mg, ultrasonicly make it fully dissolve; Under magnetic stirring, then be that the DEG solution of sodium acetate of 0.2g/mL is added drop-wise in above-mentioned dispersion liquid by 10 ± 0.5mL concentration, and stir 60 ± 10min at ambient temperature; Finally, above-mentioned mixed liquor being transferred to specification is in the water heating kettle of 50mL, is to react 10 ± 1h in the baking oven of 180 DEG C in temperature; After reaction terminates, by repeatedly centrifugation and absolute ethanol washing process, obtain black product alpha-nickel hydroxide and nickel-plating carbon nanotube composite nanorod, be placed on dry 10 ~ 12h in 60 ± 5 DEG C of baking ovens, for subsequent use;
(2) synthesis of α, β-cobalt hydroxide nickel mixture and nickel-plating carbon nanotube composite material:
Alpha-nickel hydroxide and the nickel-plating carbon nanotube composite nanorod powder of 80 ± 1mg previous step prepared join ultrasonic 10 ~ 20min in distilled water, be allowed to condition in water and be uniformly dispersed, then the cobalt chloride hexahydrate 0.238 ± 0.005mg added, at room temperature magnetic agitation 10 ~ 20min, makes it dissolve completely; Above-mentioned mixed liquor being transferred to specification is in the water heating kettle of 50ml, is to react 60 ± 5min in the baking oven of 120 DEG C in temperature; After reaction terminates, obtain black product α, β-cobalt hydroxide nickel mixture and nickel-plating carbon nanotube composite material by repeatedly centrifugation and absolute ethanol washing process, be placed on drying 10 ~ 12h in 60 ± 5 DEG C of baking ovens, for subsequent use;
(3) synthesis of β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material:
Be the α that the previous step adding 40 ± 0.5mg in the sodium hydroxide solution of 0.1mol/L prepares in 40 ± 1ml concentration, β-cobalt hydroxide nickel mixture and nickel-plating carbon nanotube composite material, ultrasonic 10 ~ 15min, afterwards at room temperature magnetic agitation 10 ~ 20min, make it fully dissolve; The product dissolved being inserted specification is in the water heating kettle of 50ml, is to react 60 ± 5min in the baking oven of 180 DEG C in temperature; After reaction terminates, obtain black end-product β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material by repeatedly centrifugation and absolute ethanol washing process, be placed on drying 10 ~ 12h in 60 ± 5 DEG C of baking ovens, for subsequent use.
The β prepared by said method-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material have three-dimensional multistage structure.
β prepared by the present invention-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material, there is excellent specific capacity, high rate performance and cycle performance, as the electrode material of ultracapacitor, show excellent specific capacity, under the current density of 1Ag-1, material specific capacity is up to 1982Fg
-1, the capability retention of 1000 circles that circulate under this electric current is 86.8%.In addition, the preparation cost of this nano material is low, efficiency is high, is easier to industry and amplifies to solve actual application problem.
Above-mentioned β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material, as electrode material, can be used for preparing ultracapacitor.Concrete steps are:
Active material (β-cobalt hydroxide nickel and the nickel-plating carbon nanotube composite material of preparation), binding agent (polytetrafluoroethylene aqueous dispersion of 10%) and conductive agent (acetylene black) are mixed with the mass ratio of 80:10:10.Again the purees obtained is transferred on hand roller milling train, repeatedly roll-in is carried out to it, until be pressed into the moderate uniform sheet of thickness, shifted after allowing, under 80 DEG C of conditions, dry 12h, form electrode foil.Electrode material thin slice good for finish-drying is carried out cutting, and the quality of the every sheet of precise, then be clipped in the middle of two panels nickel foam, with the pressure of about 10MPa, they are pressed together.Finally with spot welding machine, a nickel wire is welded on the electrode surface of pressing, forms ultracapacitor.In the test process of electrical property, select Ag/AgCl electrode as reference electrode, platinum plate electrode is as to electrode, and the KOH aqueous solution of 1mol/L is as electrolyte.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrum of three-step approach synthetic product.It is down the X-ray diffraction standard spectrum of β-cobalt hydroxide nickel.
The stereoscan photograph of Fig. 2 three-step approach synthetic product.Wherein, a and b is the stereoscan photograph of first step alpha-nickel hydroxide and nickel-plating carbon nanotube composite nanorod; C and d is the stereoscan photograph of second step intermediate product; E and f is the stereoscan photograph of end-product β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material.
The transmission electron microscope photo of Fig. 3 three-step approach synthetic product.Wherein, a and b is the transmission electron microscope photo of first step alpha-nickel hydroxide and nickel-plating carbon nanotube composite nanorod; C and d is the transmission electron microscope photo of second step intermediate product; E and f is the transmission electron microscope photo of end-product β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material.
Fig. 4 is the x-ray photoelectron spectroscopy of end-product β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material.Wherein, a is full spectrum; B is the meticulous spectrum of Ni2p; C is the meticulous spectrum of Co2p.
Fig. 5 is the Electrochemical Properties of end-product β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material.Wherein, a is the CV curve of sample under different scanning rates; B is that sample is at 1Ag
-1cycle performance under current density; C is the specific capacity of sample under different current density; D is the constant current charge-discharge curve of sample under different current density.
Fig. 6 is the EELS data being in end-product under different charging and discharging state: wherein, a is the K peak of O; B is the L of Co
3and L
2peak; C is the L of Ni
3and L
2peak.
Embodiment
β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material are obtained by following three steps:
(1) solvent-thermal process of alpha-nickel hydroxide and nickel-plating carbon nanotube composite nanorod:
First, supersonic cleaning machine is utilized to add 80 ± 1mg nickel-plating carbon nanotube in the diethylene glycol of 30 ± 1mL, ultrasonic 30 ~ 35min; Then in this suspension-turbid liquid, add Nickel dichloride hexahydrate 285 ± 5mg, ultrasonicly make it fully dissolve; Under magnetic stirring, then be that the DEG solution of sodium acetate of 0.2g/mL is added drop-wise in above-mentioned dispersion liquid by 10 ± 0.5mL concentration, and stir 60 ± 10min at ambient temperature; Finally, above-mentioned mixed liquor being transferred to specification is in the water heating kettle of 50mL, is to react 10 ± 1h in the baking oven of 180 DEG C in temperature; After reaction terminates, by repeatedly centrifugation and absolute ethanol washing process, obtain black product alpha-nickel hydroxide and nickel-plating carbon nanotube composite nanorod, be placed on dry 10 ~ 12h in 60 ± 5 DEG C of baking ovens, for subsequent use;
(2) synthesis of α, β-cobalt hydroxide nickel mixture and nickel-plating carbon nanotube composite material:
Alpha-nickel hydroxide and the nickel-plating carbon nanotube composite nanorod powder of 80 ± 1mg previous step prepared join ultrasonic 10 ~ 20min in distilled water, be allowed to condition in water and be uniformly dispersed, then the cobalt chloride hexahydrate 0.238 ± 0.005mg added, at room temperature magnetic agitation 10 ~ 20min, makes it dissolve completely; Above-mentioned mixed liquor being transferred to specification is in the water heating kettle of 50ml, is to react 60 ± 5min in the baking oven of 120 DEG C in temperature; After reaction terminates, obtain black product α, β-cobalt hydroxide nickel mixture and nickel-plating carbon nanotube composite material by repeatedly centrifugation and absolute ethanol washing process, be placed on drying 10 ~ 12h in 60 ± 5 DEG C of baking ovens, for subsequent use;
(3) synthesis of β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material:
Be the α that the previous step adding 40 ± 0.5mg in the sodium hydroxide solution of 0.1mol/L prepares in 40 ± 1ml concentration, β-cobalt hydroxide nickel mixture and nickel-plating carbon nanotube composite material, ultrasonic 10 ~ 15min, afterwards at room temperature magnetic agitation 10 ~ 20min, make it fully dissolve; The product dissolved being inserted specification is in the water heating kettle of 50ml, is to react 60 ± 5min in the baking oven of 180 DEG C in temperature; After reaction terminates, obtain black end-product β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material by repeatedly centrifugation and absolute ethanol washing process, be placed on drying 10 ~ 12h in 60 DEG C of baking ovens, for subsequent use.
The pattern of β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material and size are by scanning electron microscopy (SEM, HitachiFE-SEMS-4800operatedat1kV) characterizing, is directly the sample powder of oven dry be sprinkled upon on conducting resinl to make.The electron energy loss spectroscopy (EELS) (EELS) of β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material and Microstructure Information are by transmitted electron Electronic Speculum (TEM, JEOLJEM-2100Foperatedat200kV) characterize, the sample of transmission electron microscope be by sample dispersion in ethanolic solution, then drip 6 μ L solution and support to carbon copper mesh makes.X-difraction spectrum records on BrukerD8X-raydiffractometer (Germany) withNi-filtereCuKRradiationoperatedat40kVand40mA.X-ray photoelectron spectroscopy is characterized by KratosAxisUltraDLD, and full spectrum tests logical energy 160, the logical energy 40 of meticulous spectrum test.The chemical property of β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material is by electrochemical workstation (CHI660D, Shanghai Chen Hua Instrument Ltd.) test sign, select Ag/AgCl electrode as reference electrode, platinum plate electrode is as to electrode, and the KOH aqueous solution of 1mol/L is as electrolyte.
Fig. 1 is X-ray diffraction (XRD) analysis that in three-step approach synthesis, each step obtains product.It reflects the information such as the crystalline phase of product, purity, crystallinity.Wherein, blue curve is the diffraction curve of first step product alpha-nickel hydroxide and nickel-plating carbon nanotube composite nanorod.The diffraction maximum being positioned at 26.1 and 44.6 ° belongs to (002) crystal face of carbon nano-tube and (111) crystal face of metallic nickel respectively, and all the other diffraction maximums being positioned at 10.8 °, 33.5 °, 34.5 ° and 59.7 ° correspond respectively to (003), (101), (012) and (110) crystal face of alpha-nickel hydroxide (corresponding standard card is numbered JCPDSNo.38-0715).This demonstrates the successful synthesis of alpha-nickel hydroxide and nickel-plating carbon nanotube composite nanorod.Consider that alpha-nickel hydroxide is unstable in alkaline environment, easily change into β-nickel hydroxide, the destruction of structure and pattern can be caused, have a strong impact on the chemical property of electrode material, the alpha-nickel hydroxide that we prepare solvent thermal process and nickel-plating carbon nanotube composite material have carried out hydrothermal treatment consists, utilize the method for phase in version, are translated into β-nickel hydroxide and nickel-plating carbon nanotube, and a small amount of cobalt ions that will adulterate, improve electrical property.Red curve shows, the product after second step hydrothermal treatment consists, and be the mixture of alpha-nickel hydroxide and nickel-plating carbon nanotube and β-cobalt hydroxide nickel and nickel-plating carbon nanotube, alpha-nickel hydroxide and nickel-plating carbon nanotube also do not eliminate in this step.3rd step in the basic conditions, after the hydrothermal treatment consists of 1h, the diffraction maximum belonging to alpha-nickel hydroxide disappears completely, except corresponding to the diffraction maximum of (002) crystal face of carbon nano-tube and (111) crystal face of metallic nickel, emerging diffraction maximum all belongs to β-cobalt hydroxide nickel (corresponding standard card is numbered JCPDSNo.14-0117), they are positioned at 19.2 °, 33.1 °, 38.5 °, 52.1 °, 59.0 °, 62.7 °, 70.5 ° and 72.7 °, correspond respectively to (001), (100), (101), (102), (110), (111), and (201) crystal face (103).Show that the degree of crystallinity of end-product β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material is higher and crystalline phase is purer.
Fig. 2 a-f is the pattern being characterized each step synthetic product by ESEM (SEM).Before compound, the diameter of Ni-CNTs is between 50nm to 100nm; The first step after compound, the diameter of alpha-nickel hydroxide and nickel-plating carbon nanotube is between 500nm to 600nm, and that is the thickness of alpha-nickel hydroxide is between 200nm to 250nm.Obviously can be found out the coated densification very of alpha-nickel hydroxide on nickel-plating carbon nanotube, continuously, almost there is no exposed carbon nano-tube by Fig. 2 a and 2b.This is because the compatibility of metal nickel dam and alpha-nickel hydroxide is fine, be very beneficial for the growth of alpha-nickel hydroxide on metal nickel dam surface.The carbon nano-tube that minute quantity is exposed, be because nickel-plating carbon nanotube exists not caused by the defect that metal nickel dam is coated of minute quantity, this also shows do not have the carbon nano tube surface of modification to be difficult to realize the growth of alpha-nickel hydroxide simultaneously.Fig. 2 c and 2d is the pattern photo of second step intermediate product, substantially maintains shape characteristic and the size of previous step.Fig. 2 e and 2f is the pattern photo of end-product β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material, can obviously find out, after hydrothermal treatment consists under alkali condition, except the change of crystal structure, the pattern of product also there occurs certain change.β-cobalt hydroxide nickel the nano flake be wrapped in outside nickel-plating carbon nanotube becomes more smooth and loose, and the infiltration for electrolyte provides sufficient space, significantly improves the ion transportation in electrochemical reaction.
Transmission electron microscope photo is the above-mentioned experimental result of sufficient proof more.Shown in Fig. 3 a-f, pass through three-step reaction, product changes β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material into by alpha-nickel hydroxide and nickel-plating carbon nanotube composite material, the transformation of cobalt doped and crystalline phase does not affect the overall pattern of material, it is very stable that coated nanoscale twins three-dimensional multistage structure maintains, and is not easily destroyed.The most significantly change is that the laminated structure of the nano flake grown on nickel-plating carbon nanotube surface is more more smooth and loose, and thickness is between 5 ~ 10nm.
The present invention utilizes x-ray photoelectron spectroscopy (XPS) to analyze the composition information of end-product further.Fig. 4 a is full spectrum, and Fig. 4 b and 4c is respectively the meticulous spectrum of characteristic peak of Ni and Co element.Can find out in Fig. 4 a, in end-product β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material, only contain these four kinds of elements of C, O, Co, Ni, without other impurity.In Fig. 4 b, at two characteristic peaks corresponding Ni respectively of 871.8eV and 854.2eV
2+2p
1/2and 2p
3/2. in Fig. 4 c, at two characteristic peaks corresponding Co respectively of 796.6eV and 779.9eV
2+2p
1/2and 2p
3/2.By calculating, the mass ratio of Ni and Co is 4.5:1.Demonstrate Co to be successfully entrained in β-nickel hydroxide and nickel-plating carbon nanotube composite material, and do not destroy the three-dimensional multistage lamellar structure of material.
β-cobalt hydroxide nickel is typical fake capacitance material, and the CV curve of end-product has clear and definite redox peak, as shown in Figure 5 a.The peak of this pair electric current corresponds to β-Ni (OH)
2and the reversible redox reaction between β-NiOOH:
,
Even if at 30mVs
-1under, redox peak intensity is still very high, too large displacement does not occur, shows that the equivalent resistance of synthesized β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material is very little.And sample shows good cycle performance (Fig. 5 b), after circulation 1000 is enclosed, sample does not show obvious capacity and declines, and its capability retention is about 86.8%.This is because β-stability of cobalt hydroxide nickel own is relatively good, the multilevel hierarchy of β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material is also very stable simultaneously.On nickel-plating carbon nanotube surface, between β-cobalt hydroxide nickel nano flake, there is certain gap, even if there is volumetric expansion, between nano flake, also serious collision and extruding can not occur.Fig. 5 c is the specific capacity of sample under different current density.At 2Ag
-1current density under, sample shows the highest specific capacity 1982.2Fg
-1.Along with the increase of current density, its specific capacity declines gradually, 2,5,10 and 20Ag
-1current density under, its specific capacity is respectively 1838.2,1543.8,1193.4 and 748.3Fg
-1.Simultaneously in constant current charge-discharge process, at 1Ag
-1current density under, sample has more flat charging/discharging voltage platform at about 0.3V, as fig 5d.As the current density increases, there is not significantly change in the position of charging/discharging voltage platform, illustrates that the conductivity of composite material is fine, ion diffuse is fast, equivalent resistance is little.
We utilize transmission electron microscope electron energy loss spectroscopy (EELS) (EELS) technology to carry out research and analysis to being in Ni and the Co oxidation state of sample under original state, charging and discharging state.In charge and discharge process, there occurs significant change as can be seen from the hybridization state of Fig. 6 a, O, these changes are presented as the change at OK peak in EELS.Charge and discharge process can regard Ni (OH) as
2and the reversible transition between NiOOH, wherein O is with OH
-and O
2-two kinds of forms exist.After charging, O changes 2p state into by the 1s state of original state, moves at (peak 1) to high energy direction.After peak 2 and peak 3 show sample charging, O changes Lacking oxygen into by the 1s state of original state.After electric discharge terminates, peak intensity but still higher than original state peak intensity, shows to still have O in sample
2-residual, NiOOH is not reduced completely.In Fig. 6 b and 6c, the EELS collection of illustrative plates of Co and Ni reflects the variation of valence of element before and after discharge and recharge.Two p-ratio L time uncharged
3/ L
2larger.When at 10Ag
-1current density under complete charging process after, the L of Co and Ni
3/ L
2obvious increase, and L
3and L
2the position at peak is all obvious there occurs displacement to high energy direction, and this shows that the oxidation state of Co and Ni increases, Ni
2+be converted to Ni
3+, Co
2+be transformed into Co
3+/ Co
4+.Complete discharge process under same current density after, the L of Co and Ni
3/ L
2obvious reduction, simultaneously L
3and L
2the position at peak is also obvious moves to low energy direction, but, compared with original aspect product, the L after electric discharge
3/ L
2still larger, L simultaneously
3and L
2high energy region is also more partial in the position at peak.This illustrates, in this sample, the oxidation state of Co and Ni is higher than+2.0, still there is a certain amount of Ni
3+and Co
3+/ Co
4+.After electric discharge terminates, do not realize the reduction completely of NiOOH.This phenomenon can cause in charge and discharge process, and the specific capacity of electrode material can not be embodied fully, is also the key factor affecting electrode material high rate performance.
list of references
[1]Wang,G.;Zhang,L.;Zhang,J.Areviewofelectrodematerialsforelectrochemicalsupercapacitors.
ChemicalSocietyReviews.2012,41,797-828.
[2]Gao,X.P.;Yang,H.-X.Multi-electronreactionmaterialsforhighenergydensitybatteries.
Energy&EnvironmentalScience2010,3,174-189.
[3]Simon,P.;Gogotsi,Y.Materialsforelectrochemicalcapacitors.
NatureMaterials.2008,7,845-854.
[4]Yan,J.;Wang,Q.;Wei,T.;Fan,Z.RecentAdvancesinDesignandFabricationofElectrochemicalSupercapacitorswithHighEnergyDensities.
AdvancedEnergyMaterials.2014,4,1300816.
[5]Wang,H.;Casalongue,H.S.;Liang,Y.;Dai,H.Ni(OH)2NanoplatesGrownonGrapheneasAdvancedElectrochemicalPseudocapacitorMaterials.
JournaloftheAmericanChemicalSociety.2010,132,7472-7477.
[6]Jiang,H.;Zhao,T.;Li,C.;Ma,J.Hierarchicalself-assemblyofultrathinnickelhydroxidenanoflakesforhigh-performancesupercapacitors.
JournalofMaterialsChemistry.2011,21,3818-3823.
[7]Chang,J.;Xu,H.;Sun,J.;Gao,L.HighpseudocapacitancematerialpreparedviainsitugrowthofNi(OH)2nanoflakesonreducedgrapheneoxide.
JournalofMaterialsChemistry.2012,22,11146-11150.
[8]Fang,D.-L.;Chen,Z.-D.;Liu,X.;Wu,Z.-F.;Zheng,C.-H.Homogeneousgrowthofnano-sizedβ-Ni(OH)2onreducedgrapheneoxideforhigh-performancesupercapacitors.
ElectrochimicaActa.2012,81,321-329.
[9]Yang,D.;Wang,R.;He,M.;Zhang,J.;Liu,Z.Ribbon-andBoardlikeNanostructuresofNickelHydroxide:Synthesis,Characterization,andElectrochemicalProperties.
JournalofPhysicalChemistryB.2005,109,7654-7658.
[10]Wang,B.;Chen,J.S.;Wang,Z.;Madhavi,S.;Lou,X.W.GreenSynthesisofNiONanobeltswithExceptionalPseudo-CapacitiveProperties.
AdvancedEnergyMaterials.2012,2,1188-1192.
[11]Zhang,G.;Yu,L.;Hoster,H.E.;Lou,X.W.Synthesisofone-dimensionalhierarchicalNiOhollownanostructureswithenhancedsupercapacitiveperformance.
Nanoscale.2013,5,877-881.
[12]Sun,X.;Yan,C.;Chen,Y.;Si,W.;Deng,J.;Oswald,S.;Liu,L.;Schmidt,O.G.Three-Dimensionally“Curved”NiONanomembranesasUltrahighRateCapabilityAnodesforLi-IonBatterieswithLongCycleLifetimes.
AdvancedEnergyMaterials.2014,4,1300912.
[13]Xu,L.;Ding,Y.-S.;Chen,C.-H.;Zhao,L.;Rimkus,C.;Joesten,R.;Suib,S.L.3DFlowerlikeα-NickelHydroxidewithEnhancedElectrochemicalActivitySynthesizedbyMicrowave-AssistedHydrothermalMethod.
ChemistryofMaterials.2007,20,308-316.
[14]Lee,J.W.;Ahn,T.;Soundararajan,D.;Ko,J.M.;Kim,J.D.Non-aqueousapproachtothepreparationofreducedgrapheneoxide/[smallalpha]-Ni(OH)2hybridcompositesandtheirhighcapacitancebehavior.
ChemicalCommunications.2011,47,6305-6307.
[15]Jiang,H.;Li,C.;Sun,T.;Ma,J.High-performancesupercapacitormaterialbasedonNi(OH)2nanowire-MnO2nanoflakescore-shellnanostructures.
ChemicalCommunications.2012,48,2606-2608.
[16]Yuan,C.;Zhang,X.;Su,L.;Gao,B.;Shen,L.Facilesynthesisandself-assemblyofhierarchicalporousNiOnano/microsphericalsuperstructuresforhighperformancesupercapacitors.
JournalofMaterialsChemistry.2009,19,5772-5777.
[17]Lee,J.W.;Ahn,T.;Kim,J.H.;Ko,J.M.;Kim,J.D.NanosheetsbasedmesoporousNiOmicrosphericalstructuresviafacileandtemplate-freemethodforhighperformancesupercapacitors.
ElectrochimicaActa.2011,56,4849-4857.
[18]Xia,X.;Tu,J.;Wang,X.;Gu,C.;Zhao,X..HierarchicallyporousNiOfilmgrownbychemicalbathdepositionviaacolloidalcrystaltemplateasanelectrochemicalpseudocapacitormaterial.
JournalofMaterialsChemistry.2011,21,671-679.
[19]Chen,S.;Zhu,J.;Zhou,H.;Wang,X.One-stepsynthesisoflowdefectdensitycarbonnanotube-dopedNi(OH)2nanosheetswithimprovedelectrochemicalperformances.
RSCAdvances.2011,1,484-489.
[20]Yuan,C.;Yang,L.;Hou,L.;Li,J.;Sun,Y.;Zhang,X.;Shen,L.;Lu,X.;Xiong,S.;Lou,X.W.FlexibleHybridPaperMadeofMonolayerCo3O4MicrosphereArraysonrGO/CNTsandTheirApplicationinElectrochemicalCapacitors.
AdvancedFunctionalMaterials.2012,22,2560-2566.
[21]Zhu,T.;Wu,H.B.;Wang,Y.;Xu,R.;Lou,X.W.Formationof1DHierarchicalStructuresComposedofNi3S2NanosheetsonCNTsBackboneforSupercapacitorsandPhotocatalyticH2Production.
AdvancedEnergyMaterials.2012,2,1497-1502.
[22]Dubal,D.P.;Gund,G.S.;Lokhande,C.D.;Holze,R.DecorationofSpongelikeNi(OH)2NanoparticlesontoMWCNTsUsinganEasilyManipulatedChemicalProtocolforSupercapacitors.
AcsAppliedMaterials&Interfaces.2013,5,2446-2454.
[23]Huang,L.;Chen,D.;Ding,Y.;Feng,S.;Wang,Z.L.;Liu,M.Nickel–CobaltHydroxideNanosheetsCoatedonNiCo2O4NanowiresGrownonCarbonFiberPaperforHigh-PerformancePseudocapacitors.
NanoLetters.2013,13,3135-3139.
[24]Liang,M.;Zhi,L.Graphene-basedelectrodematerialsforrechargeablelithiumbatteries.
JournalofMaterialsChemistry.2009,19,5871-5878.
[25]Chen,S.;Zhu,J.;Wu,X.;Han,Q.;Wang,X.GrapheneOxide?MnO2NanocompositesforSupercapacitors.
ACSNano.2010,4,2822-2830.
[26]Yan,J.;Fan,Z.;Wei,T.;Qian,W.;Zhang,M.;Wei,F.Fastandreversiblesurfaceredoxreactionofgrapheme-MnO2compositesassupercapacitorelectrodes.
Carbon2010,48,3825-3833.
[27]Huang,X.;Zeng,Z.;Fan,Z.;Liu,J.;Zhang,H.Graphene-BasedElectrodes.
AdvancedMaterials.2012,24,5979-6004.
[28]Huang,L.M.;Wen,T.C.;Gopalan,A.Electrochemicalandspectroelectrochemicalmonitoringofsupercapacitanceandelectrochromicpropertiesofhydrousrutheniumoxideembeddedpoly(3,4-ethylenedioxythiophene)-poly(styrenesulfonicacid)composite.
ElectrochimicaActa.2006,51,3469-3476.
[29]Sharma,R.K.;Rastogi,A.C.;Desu,S.B.Manganeseoxideembeddedpolypyrrolenanocompositesforelectrochemicalsupercapacitor.
ElectrochimicaActa.2008,53,7690-7695.
[30]Xia,X.;Tu,J.;Zhang,Y.;Wang,X.;Gu,C.;Zhao,X.-b.;Fan,H.J.High-QualityMetalOxideCore/ShellNanowireArraysonConductiveSubstratesforElectrochemicalEnergyStorage.
ACSNano.2012,6,5531-5538.
[31]Yang,G.W.;Xu,C.L.;Li,H.L.Electrodepositednickelhydroxideonnickelfoamwithultrahighcapacitance.
ChemicalCommunications.2008,6537-6539.
[32]Lu,Z.;Chang,Z.;Zhu,W.;Sun,X.Beta-phasedNi(OH)2nanowallfilmwithreversiblecapacitancehigherthantheoreticalFaradiccapacitance.
ChemicalCommunications.2011,47,9651-9653.
[33]Wang,Y.;Cao,D.;Wang,G.;Wang,S.;Wen,J.;Yin,J.Sphericalclustersofβ-Ni(OH)2nanosheetssupportedonnickelfoamfornickelmetalhydridebattery.
ElectrochimicaActa.2011,56,8285-8290.
[34]Yuan,Y.F.;Xia,X.H.;Wu,J.B.;Yang,J.L.;Chen,Y.B.;Guo,S.YNickelfoam-supportedporousNi(OH)2/NiOOHcompositefilmasadvancedpseudocapacitormaterial.
ElectrochimicaActa.2011,56,2627-2632.
[35]Khan,Y.;Hussain,S.;S?derlind,F.;K?ll,P.-O.;Abbasi,M.A.;Durrani,S.K.Honeycombβ-Ni(OH)2filmsgrownon3Dnickelfoamsubstratesatlowtemperature.
MaterialsLetters.2012,69,37-40.
[36]Lv,S.;Suo,H.;Wang,J.;Wang,Y.;Zhao,C.;Xing,S.FacilesynthesisofnanostructuredNi(OH)2onnickelfoamanditselectrochemicalproperty.
ColloidsandSurfacesA:PhysicochemicalandEngineeringAspects.2012,396,292-298.
[37]Zhang,F.;Yuan,C.;Lu,X.;Zhang,L.;Che,Q.;Zhang,X.FacilegrowthofmesoporousCo3O4nanowirearraysonNifoamforhighperformanceelectrochemicalcapacitors.
JournalofPowerSources.2012,203,250-256.
[38]Ji,J.;Zhang,L.L.;Ji,H.;Li,Y.;Zhao,X.;Bai,X.;Fan,X.;Zhang,F.;Ruoff,R.S.NanoporousNi(OH)2ThinFilmon3DUltrathin-GraphiteFoamforAsymmetricSupercapacitor.
ACSNano.2013,7,6237-6243.
[39]Pandolfo,A.G.;Hollenkamp,A.F.Carbonpropertiesandtheirroleinsupercapacitors.
JournalofPowerSources.2006,157,11-27.
[40]Zhang,L.L.;Zhao,X.S.Carbon-basedmaterialsassupercapacitorelectrodes.
ChemicalSocietyReviews.2009,38,2520-2531.
[41]Dreyer,D.R.;Park,S.;Bielawski,C.W.;Ruoff,R.S.Thechemistryofgrapheneoxide.
ChemicalSocietyReviews.2010,39,228-240.。
Claims (3)
1. a preparation method for β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material, is characterized in that concrete steps are: the solvent-thermal process of (1) alpha-nickel hydroxide and nickel-plating carbon nanotube composite nanorod:
First, supersonic cleaning machine is utilized to add 80 ± 1mg nickel-plating carbon nanotube in the diethylene glycol of 30 ± 1mL, ultrasonic 30 ~ 35min; Then in this suspension-turbid liquid, add Nickel dichloride hexahydrate 285 ± 5mg, ultrasonicly make it fully dissolve; Under magnetic stirring, then be that the DEG solution of sodium acetate of 0.2g/mL is added drop-wise in above-mentioned dispersion liquid by 10 ± 0.5mL concentration, and stir 60 ± 10min at ambient temperature; Finally, above-mentioned mixed liquor being transferred to specification is in the water heating kettle of 50mL, is to react 10 ± 1h in the baking oven of 180 DEG C in temperature; After reaction terminates, by repeatedly centrifugation and absolute ethanol washing process, obtain black product alpha-nickel hydroxide and nickel-plating carbon nanotube composite nanorod, be placed on dry 10 ~ 12h in 60 ± 5 DEG C of baking ovens, for subsequent use;
(2) synthesis of α, β-cobalt hydroxide nickel mixture and nickel-plating carbon nanotube composite material:
Alpha-nickel hydroxide and the nickel-plating carbon nanotube composite nanorod powder of 80 ± 1mg previous step prepared join ultrasonic 10 ~ 20min in distilled water, be allowed to condition in water and be uniformly dispersed, then the cobalt chloride hexahydrate 0.238 ± 0.005mg added, at room temperature magnetic agitation 10 ~ 20min, makes it dissolve completely; Above-mentioned mixed liquor being transferred to specification is in the water heating kettle of 50ml, is to react 60 ± 5min in the baking oven of 120 DEG C in temperature; After reaction terminates, obtain black product α, β-cobalt hydroxide nickel mixture and nickel-plating carbon nanotube composite material by repeatedly centrifugation and absolute ethanol washing process, be placed on drying 10 ~ 12h in 60 ± 5 DEG C of baking ovens, for subsequent use;
(3) synthesis of β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material:
Be the α that the previous step adding 40 ± 0.5mg in the sodium hydroxide solution of 0.1mol/L prepares in 40 ± 1ml concentration, β-cobalt hydroxide nickel mixture and nickel-plating carbon nanotube composite material, ultrasonic 10 ~ 15min, afterwards at room temperature magnetic agitation 10 ~ 20min, make it fully dissolve; The product dissolved being inserted specification is in the water heating kettle of 50ml, is to react 60 ± 5min in the baking oven of 180 DEG C in temperature; After reaction terminates, obtain black end-product β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material by repeatedly centrifugation and absolute ethanol washing process, be placed on drying 10 ~ 12h in 60 ± 5 DEG C of baking ovens, for subsequent use.
2. the β prepared by preparation method described in claim 1-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material, in the nano bar-shape of three-dimensional multistage structure, the flower-like nanometer thin slice vertical-growth of β-cobalt hydroxide nickel is on nickel-plating carbon nanotube surface.
3. β-cobalt hydroxide nickel as claimed in claim 2 and nickel-plating carbon nanotube composite material are as the application of electrode material in ultracapacitor.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106449153A (en) * | 2016-10-18 | 2017-02-22 | 北京化工大学 | Nano Ni (OH)2@C composite material and preparation method |
| CN110534748A (en) * | 2019-08-29 | 2019-12-03 | 东北大学 | A kind of preparation method of flexible lithium ion battery negative battery collector |
| CN111180216A (en) * | 2020-01-15 | 2020-05-19 | 兰州理工大学 | Composite material for super capacitor and preparation method thereof |
| CN112053855A (en) * | 2020-08-28 | 2020-12-08 | 中南林业科技大学 | Electrode material based on multi-walled carbon nanotube-carbonized wood mixed support, preparation method and supercapacitor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1588676A (en) * | 2004-09-21 | 2005-03-02 | 清华大学 | Method for coating and mixing metal M alpha-Co(OH)2 on ball shape nickel hydroxide surface |
| CN102509628A (en) * | 2011-09-29 | 2012-06-20 | 南开大学 | Nanometre Ni(OH)2 and Co(OH)2 composite material for super-capacitor and preparation method of nanometre Ni(OH)2 and Co(OH)2 composite material |
| CN102544477A (en) * | 2012-01-04 | 2012-07-04 | 广州市云通磁电有限公司 | Preparation method of cobalt-clad nanometer alpha-nickel hydroxide |
-
2016
- 2016-01-20 CN CN201610036643.0A patent/CN105551818B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1588676A (en) * | 2004-09-21 | 2005-03-02 | 清华大学 | Method for coating and mixing metal M alpha-Co(OH)2 on ball shape nickel hydroxide surface |
| CN102509628A (en) * | 2011-09-29 | 2012-06-20 | 南开大学 | Nanometre Ni(OH)2 and Co(OH)2 composite material for super-capacitor and preparation method of nanometre Ni(OH)2 and Co(OH)2 composite material |
| CN102544477A (en) * | 2012-01-04 | 2012-07-04 | 广州市云通磁电有限公司 | Preparation method of cobalt-clad nanometer alpha-nickel hydroxide |
Non-Patent Citations (1)
| Title |
|---|
| XIAOWEI MA等: "Ultrathin β-Ni(OH)2 Nanoplates Vertically Grown on Nickel-Coated Carbon Nanotubes as High-Performance Pseudocapacitor Electrode Materials", 《ACS APPL.MATER.INTERFACES》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106449153A (en) * | 2016-10-18 | 2017-02-22 | 北京化工大学 | Nano Ni (OH)2@C composite material and preparation method |
| CN106449153B (en) * | 2016-10-18 | 2018-10-23 | 北京化工大学 | A kind of Ni nanoparticle (OH)2@C composites and preparation method |
| CN110534748A (en) * | 2019-08-29 | 2019-12-03 | 东北大学 | A kind of preparation method of flexible lithium ion battery negative battery collector |
| CN111180216A (en) * | 2020-01-15 | 2020-05-19 | 兰州理工大学 | Composite material for super capacitor and preparation method thereof |
| CN112053855A (en) * | 2020-08-28 | 2020-12-08 | 中南林业科技大学 | Electrode material based on multi-walled carbon nanotube-carbonized wood mixed support, preparation method and supercapacitor |
| CN112053855B (en) * | 2020-08-28 | 2022-03-04 | 中南林业科技大学 | Electrode material based on multi-walled carbon nanotube-carbonized wood mixed support, preparation method and supercapacitor |
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