CN104795245A - Wire-shaped nickel cobalt oxide@nickel cobalt sulfide hetero-structure composite, and preparation method and purpose thereof - Google Patents
Wire-shaped nickel cobalt oxide@nickel cobalt sulfide hetero-structure composite, and preparation method and purpose thereof Download PDFInfo
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- CN104795245A CN104795245A CN201510140593.6A CN201510140593A CN104795245A CN 104795245 A CN104795245 A CN 104795245A CN 201510140593 A CN201510140593 A CN 201510140593A CN 104795245 A CN104795245 A CN 104795245A
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- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 47
- 239000006260 foam Substances 0.000 claims abstract description 42
- 239000002070 nanowire Substances 0.000 claims abstract description 31
- 239000007772 electrode material Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000005349 anion exchange Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 16
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 11
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000009156 water cure Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 4
- SQWOZZOPVKWYMP-UHFFFAOYSA-N [Ni].[Co]=S.[Co]=O.[Ni] Chemical compound [Ni].[Co]=S.[Co]=O.[Ni] SQWOZZOPVKWYMP-UHFFFAOYSA-N 0.000 claims 2
- 239000003990 capacitor Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000000992 sputter etching Methods 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 description 14
- 238000007599 discharging Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010408 sweeping Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 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
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- H01G11/22—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
- H01G11/84—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)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a wire-shaped nickel cobalt oxide@nickel cobalt sulfide hetero-structure composite, and a preparation method and purpose thereof. The wire-shaped nickel cobalt oxide@nickel cobalt sulfide hetero-structure composite has the advantages that the composite uses nickel cobalt oxide nanowires as a framework, and an anion exchange method is used to convert the nickel cobalt oxide nanowires into the nickel cobalt oxide@nickel cobalt sulfide nanowires which are large in surface area and good in conductivity and flexibility through sulfur ion etching; the preparation of the nanowires uses a hydrothermal method and an in-situ growth method, the nanowires which structurally vertically grow are neat in arrangement and has a regular three-dimensional hetero-structure; compared with the prior art, the composite prepared by the method is high in purity, good in dispersity, good crystal form, controllable, low in production cost and good in reproducibility; the prepared composite grows on foam nickel and can be directly used as the electrode material of super capacitors, and long circulation stability, large specific capacitance, high energy density and power density and high commercial value are achieved.
Description
Technical field
The present invention relates to technical field of nano material, be specifically related to a kind of preparation method and application thereof of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material.
Background technology
The development of advancing by leaps and bounds along with science and technology and the update of electronic product, the research of electrode material for super capacitor has caused the great interest of researchers.At present, traditional electrode material for super capacitor mainly contains following a few class: material with carbon element class electrode material, metal oxide-type electrode material, conducting polymer class electrode material.But, in actual applications, it is found that, more or less all there is respective defect in these traditional electrode materials, as: active area is little, and poorly conductive, capacitance are low, circulation timei is short, energy density and power density little, due to the existence of these defects, be difficult to meet application demand higher in reality.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material, obtained material can directly as the electrode material of ultracapacitor.Present invention also offers a kind of application of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material.A kind of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material provided by the invention, with nickel cobalt oxide nano wire for skeleton, utilize anion exchange method, by nickel cobalt oxide nano wire, by the etching of sulphion, be converted into surface area larger, conductivity, flexible better nickel cobalt sulfide nanometer linear.The method preparing employing hydro-thermal, growth in situ of this nano wire, the growth of its structure vertical, marshalling, the well-regulated 3-D heterojunction structure of tool.Concrete technical scheme is as follows:
A preparation method for wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material, comprises the following steps:
(1) nickel foam is cleaned;
(2) by the mixed liquor of redistilled water, six water nickel chlorides, CoCL2 6H2O, urea and ammonium fluoride, add in reactor, the nickel foam after cleaning is immersed in mixed liquor, reaction, dry, namely obtain and grow the nickel foam of nickel cobalt oxide nano wire;
(3) prepare nine water cure sodium mixed solutions, the nickel foam growing nickel cobalt oxide nano wire step (2) prepared immerses mixed solution, and reaction is dry, i.e. obtained nickel cobalt oxide@nickel cobalt sulfide heterogeneous structural nano wire material.
Further, in step (1), the nickel foam of impurity is had on surface to clean up.
Further, in step (2), redistilled water, six water nickel chlorides, CoCL2 6H2O, urea and ammonium fluoride are mixed, obtains mixed liquor, add in reactor, nickel foam after cleaning is immersed in mixed liquor, reactor is airtight, at 100-150 DEG C, react 4-10h, be cooled to room temperature, cleaning, drying at room temperature, namely obtains and grows the nickel foam of nickel cobalt oxide nano wire.
Further, in step (3), be dissolved in redistilled water by nine water cure sodium, form uniform mixed solution, the nickel foam growing nickel cobalt oxide nano wire prepared by step b immerses mixed solution, reactor is airtight, at 100-150 DEG C, react 2-6h, be cooled to room temperature, cleaning, dry 2h at 100 DEG C, i.e. obtained nickel cobalt oxide@nickel cobalt sulfide heterogeneous structural nano wire material.
Further, in step (1), surface is had the nickel foam of impurity puts into ethanol successively, acetone, watery hydrochloric acid, redistilled water carry out ultrasonic cleaning, the ultrasonic cleaning time is respectively 10-20min.
Further, in step (2), in the mixed solution obtained, concentration >=the 0.008mol/L of six water nickel chlorides, the concentration >=0.016mol/L of CoCL2 6H2O, the concentration >=0.040mol/L of urea, concentration >=the 0.008mol/L of ammonium fluoride, the volume >=25mL of redistilled water.
Further, in step (3), nine water cure sodium concentration in mixed liquor is 0.01-0.03mol/L.
A kind of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material, with nickel cobalt oxide nano wire for skeleton, utilize anion exchange method, by nickel cobalt oxide nano wire, by the etching of sulphion, be converted into nickel cobalt oxide@nickel cobalt sulfide nanometer linear.
Further, above-mentioned method is adopted to prepare.
The purposes of above-mentioned wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material, as the electrode material of ultracapacitor.
Compared with currently available technology, the method of a kind of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material provided by the invention, in airtight high-temperature high-pressure reaction kettle, adopt redistilled water as reaction dissolvent, add six water nickel chlorides, CoCL2 6H2O, urea and ammonium fluoride mix, by heating reaction system, produce a hyperbaric environment and prepare cobalt acid zinc nano-material, subsequently, adopt redistilled water as reaction dissolvent, add nine water cure sodium, solution is mixed, nickel cobalt oxide nano-material prepared by foam nickel base is immersed mixed solution, produce hyperbaric environment by heating reaction system and prepare a kind of effective ways of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material.Compare with prior art, preparation method's product purity provided by the invention be high, good dispersion, good crystalline and can control, production cost is low, favorable reproducibility.Prepared wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material growth is in nickel foam, can directly as the electrode material of ultracapacitor, achieve long cyclical stability, large concrete electric capacity, high energy density and power density, as the electrode material of ultracapacitor, there is in stored energy potential using value.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph (SEM) of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material prepared by embodiment 1;
Fig. 2 is the electron scanning micrograph (SEM) of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material prepared by embodiment 1;
Fig. 3 is the X-ray diffraction photo (XRD) of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material prepared by embodiment 1;
Fig. 4 is the transmission electron microscope photo (TEM) that embodiment 1 prepares wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material;
Fig. 5 is the electron scanning micrograph (SEM) of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material prepared by embodiment 2;
Fig. 6 is the electron scanning micrograph (SEM) of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material prepared by embodiment 3;
Fig. 7 is the electron scanning micrograph (SEM) of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material prepared by embodiment 4;
Fig. 8 is the electron scanning micrograph (SEM) of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material prepared by embodiment 5;
Fig. 9 is the cyclic voltammetry curve (CV) of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material prepared by embodiment 1;
Figure 10 is the charging and discharging curve of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material prepared by embodiment 1;
Figure 11 is the wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material of embodiment 1 preparation and the concrete electric capacity/area capacitance-current density plot comparison diagram of nickel cobalt oxide nano-material.
Embodiment
Describe the present invention with reference to the accompanying drawings below, it is a kind of preferred embodiment in numerous embodiments of the present invention.
In one embodiment, a kind of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material, with nickel cobalt oxide nano wire for skeleton, utilize anion exchange method, by nickel cobalt oxide nano wire, by the etching of sulphion, be converted into surface area larger, conductivity, flexible better nickel cobalt oxide@nickel cobalt sulfide nanometer linear.The method preparing employing hydro-thermal, growth in situ of this nano wire, the growth of its structure vertical, marshalling, the well-regulated 3-D heterojunction structure of tool.
Preparation method comprises the following steps:
A, have the nickel foam of impurity to clean up on surface: surface to be had the nickel foam of impurity puts into ethanol successively, acetone, watery hydrochloric acid, redistilled water carry out ultrasonic cleaning, the ultrasonic cleaning time is respectively 10-20min.
B, by redistilled water, six water nickel chlorides, CoCL2 6H2O, urea and ammonium fluoride mix, obtain mixed liquor, add in reactor, nickel foam after cleaning is immersed in mixed liquor, reactor is airtight, 4-10h is reacted at 100-150 DEG C, be cooled to room temperature, cleaning, drying at room temperature, namely obtain and grow the nickel foam of nickel cobalt oxide nano wire, in the mixed solution obtained in step b, concentration >=the 0.008mol/L of six water nickel chlorides, concentration >=the 0.016mol/L of CoCL2 6H2O, concentration >=the 0.040mol/L of urea, concentration >=the 0.008mol/L of ammonium fluoride, volume >=the 25mL of redistilled water,
C, nine water cure sodium are dissolved in redistilled water, form uniform mixed solution, the nickel foam growing nickel cobalt oxide nano wire prepared by step b immerses mixed solution, reactor is airtight, at 100-150 DEG C, react 2-6h, be cooled to room temperature, cleaning, dry 2h at 100 DEG C, i.e. obtained nickel cobalt oxide@nickel cobalt sulfide heterogeneous structural nano wire material.Nine water cure sodium concentration in mixed liquor is 0.01-0.03mol/L.
Embodiment 1
A preparation method for wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material, comprises the following steps:
A, surface had the nickel sheet of impurity puts into ethanol successively, acetone, watery hydrochloric acid, redistilled water carry out ultrasonic cleaning 15min;
B, 25mL redistilled water, 0.2mmol six water nickel chloride, 0.4mmol CoCL2 6H2O, 1mmol urea and 0.4mmol ammonium fluoride are mixed after add in 100mL reactor, the nickel foam processed is immersed in mixed liquor, tighten kettle cover, 8h is reacted at 120 DEG C, take out reactor and naturally cool to room temperature, rinse well with ethanol, redistilled water successively, drying at room temperature, namely obtain and grow the nickel foam of nickel cobalt oxide nano-material.
C, 0.4mmol vulcanized sodium is dissolved in 25mL redistilled water, stir and form uniform mixed solution, the nickel foam growing nickel cobalt oxide nano-material by above-mentioned preparation immerses mixed solution, reactor is airtight, at 120 DEG C, react 3h, be cooled to room temperature, cleaning, then dry 2h at 100 DEG C, i.e. obtained wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material.
An application for wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material, as the electrode material of ultracapacitor.
As shown in Figure 2, this heterostructure composite material vertical-growth is on the surface of nickel foam, and arrangement evenly, in 3-D heterojunction structure for the pattern of made wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material.
Get 10mL 0.1M NaOH solution and put into electrolysis tank as electrolyte solution, using the wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material of preparation in embodiment 1 as work electrode, sweep speed for 5mV s
-1time survey cyclic voltammetry curve (in Fig. 9 curve 1), then sweeping speed for 10mV s
-1time survey cyclic voltammetry curve (in Fig. 9 curve 2), the like obtain sweeping speed for 20mV s
-1(in Fig. 9 curve 3), 50mV s
-1(in Fig. 9 curve 4), 100mV s
-1(in Fig. 9 curve 5), as can be seen from the CV figure obtained, along with the increase voltage linear relation of sweeping speed.
Get 10mL 0.1M NaOH solution and put into electrolysis tank as electrolyte solution, using the wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material of preparation in embodiment 1 as work electrode, at 5mA cm
-2time obtain charging and discharging curve (in Figure 10 curve 1), at 10mA cm
-2time obtain charging and discharging curve (in Figure 10 curve 2), at 15mA cm
-2time obtain charging and discharging curve (in Figure 10 curve 3), at 20mA cm
-2time obtain charging and discharging curve (in Figure 10 curve 4), at 30mA cm
-2time obtain charging and discharging curve (in Figure 10 curve 5), at 50mA cm
-2time obtain charging and discharging curve (in Figure 10 curve 6), can show that wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material compares other material capacity as electrode material from charging and discharging curve larger.Be 5mA cm by calculating in current density
-2time, maximum concrete electric capacity is 2424F g
-1, corresponding area capacitance is 4.8F cm
-2, considerably beyond nickel cobalt oxide nano line electrode material.
Embodiment 2
A preparation method for wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material, comprises the following steps:
A, surface had the nickel sheet of impurity puts into ethanol successively, acetone, watery hydrochloric acid, redistilled water carry out ultrasonic cleaning 15min;
B, 25mL redistilled water, 0.2mmol six water nickel chloride, 0.4mmol CoCL2 6H2O, 2mmol urea and 0.4mmol ammonium fluoride are mixed after add in 100mL reactor, the nickel foam processed is immersed in mixed liquor, tighten kettle cover, 10h is reacted at 150 DEG C, take out reactor and naturally cool to room temperature, rinse well with ethanol, redistilled water successively, drying at room temperature, namely obtain and grow the nickel foam of nickel cobalt oxide nano-material.
C, 0.25mmol vulcanized sodium is dissolved in 25mL redistilled water, stir and form uniform mixed solution, the nickel foam growing nickel cobalt oxide nano-material by above-mentioned preparation immerses mixed solution, reactor is airtight, at 110 DEG C, react 3h, be cooled to room temperature, cleaning, then dry 2h at 100 DEG C, i.e. obtained wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material.
An application for wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material, as the electrode material of ultracapacitor.
Embodiment 3
A preparation method for wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material, comprises the following steps:
A, surface had the nickel sheet of impurity puts into ethanol successively, acetone, watery hydrochloric acid, redistilled water carry out ultrasonic cleaning 15min;
B, 25mL redistilled water, 0.2mmol six water nickel chloride, 0.6mmol CoCL2 6H2O, 1mmol urea and 0.5mmol ammonium fluoride are mixed after add in 100mL reactor, the nickel foam processed is immersed in mixed liquor, tighten kettle cover, 8h is reacted at 140 DEG C, take out reactor and naturally cool to room temperature, rinse well with ethanol, redistilled water successively, drying at room temperature, namely obtain and grow the nickel foam of nickel cobalt oxide nano-material.
C, 0.6mmol vulcanized sodium is dissolved in 25mL redistilled water, stir and form uniform mixed solution, the nickel foam growing nickel cobalt oxide nano-material by above-mentioned preparation immerses mixed solution, reactor is airtight, at 150 DEG C, react 5h, be cooled to room temperature, cleaning, then dry 2h at 100 DEG C, i.e. obtained nickel cobalt oxide@nickel cobalt sulfide heterogeneous structural nano wire material.
An application for wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material, as the electrode material of ultracapacitor.
Embodiment 4
A preparation method for wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material, comprises the following steps:
A, surface had the nickel sheet of impurity puts into ethanol successively, acetone, watery hydrochloric acid, redistilled water carry out ultrasonic cleaning 15min;
B, 25mL redistilled water, 0.3mmol six water nickel chloride, 0.4mmol CoCL2 6H2O, 1mmol urea and 0.4mmol ammonium fluoride are mixed after add in 100mL reactor, the nickel foam processed is immersed in mixed liquor, tighten kettle cover, 8h is reacted at 130 DEG C, take out reactor and naturally cool to room temperature, rinse well with ethanol, redistilled water successively, drying at room temperature, namely obtain and grow the nickel foam of nickel cobalt oxide nano-material.
C, 0.75mmol vulcanized sodium is dissolved in 25mL redistilled water, stir and form uniform mixed solution, the nickel foam growing nickel cobalt oxide nano-material by above-mentioned preparation immerses mixed solution, reactor is airtight, at 140 DEG C, react 6h, be cooled to room temperature, cleaning, then dry 2h at 100 DEG C, i.e. obtained wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material.
An application for wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material, as the electrode material of ultracapacitor.
Embodiment 5
A preparation method for wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material, comprises the following steps:
A, surface had the nickel sheet of impurity puts into ethanol successively, acetone, watery hydrochloric acid, redistilled water carry out ultrasonic cleaning 15min;
B, 25mL redistilled water, 0.2mmol six water nickel chloride, 0.4mmol CoCL2 6H2O, 1mmol urea and 0.4mmol ammonium fluoride are mixed after add in 100mL reactor, the nickel foam processed is immersed in mixed liquor, tighten kettle cover, 6h is reacted at 100 DEG C, take out reactor and naturally cool to room temperature, rinse well with ethanol, redistilled water successively, drying at room temperature, namely obtain and grow the nickel foam of nickel cobalt oxide nano-material.
C, 0.25mmol vulcanized sodium is dissolved in 35mL redistilled water, stir and form uniform mixed solution, the nickel foam growing nickel cobalt oxide nano-material by above-mentioned preparation immerses mixed solution, reactor is airtight, at 100 DEG C, react 2h, be cooled to room temperature, cleaning, then dry 2h at 100 DEG C, i.e. obtained wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material.
An application for wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material, as the electrode material of ultracapacitor.
Above by reference to the accompanying drawings to invention has been exemplary description; obvious specific implementation of the present invention is not subject to the restrictions described above; as long as have employed the various improvement that method of the present invention is conceived and technical scheme is carried out; or directly apply to other occasion, all within protection scope of the present invention without improving.
Claims (10)
1. a preparation method for wire nickel cobalt oxide nickel cobalt sulfide heterostructure composite material, is characterized in that, comprise the following steps:
(1) nickel foam is cleaned;
(2) by the mixed liquor of redistilled water, six water nickel chlorides, CoCL2 6H2O, urea and ammonium fluoride, add in reactor, the nickel foam after cleaning is immersed in mixed liquor, reaction, dry, namely obtain and grow the nickel foam of nickel cobalt oxide nano wire;
(3) prepare nine water cure sodium mixed solutions, the nickel foam growing nickel cobalt oxide nano wire step (2) prepared immerses mixed solution, and reaction is dry, i.e. obtained nickel cobalt oxide@nickel cobalt sulfide heterogeneous structural nano wire material.
2. the preparation method of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material as claimed in claim 1, is characterized in that, in step (1), being had on surface the nickel foam of impurity to clean up.
3. the preparation method of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material as claimed in claim 1 or 2, it is characterized in that, in step (2), redistilled water, six water nickel chlorides, CoCL2 6H2O, urea and ammonium fluoride are mixed, obtain mixed liquor, add in reactor, nickel foam after cleaning is immersed in mixed liquor, reactor is airtight, at 100-150 DEG C, react 4-10h, be cooled to room temperature, cleaning, drying at room temperature, namely obtains and grows the nickel foam of nickel cobalt oxide nano wire.
4. the preparation method of the wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material according to any one of claim 1-3, it is characterized in that, in step (3), nine water cure sodium are dissolved in redistilled water, form uniform mixed solution, the nickel foam growing nickel cobalt oxide nano wire prepared by step b immerses mixed solution, reactor is airtight, 2-6h is reacted at 100-150 DEG C, be cooled to room temperature, cleaning, dry 2h at 100 DEG C, i.e. obtained nickel cobalt oxide@nickel cobalt sulfide heterogeneous structural nano wire material.
5. the preparation method of the wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material according to any one of claim 1-4, it is characterized in that, in step (1), surface is had the nickel foam of impurity puts into ethanol successively, acetone, watery hydrochloric acid, redistilled water carry out ultrasonic cleaning, the ultrasonic cleaning time is respectively 10-20min.
6. the preparation method of the wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material according to any one of claim 1-5, it is characterized in that, in step (2), in the mixed solution obtained, concentration >=the 0.008mol/L of six water nickel chlorides, the concentration >=0.016mol/L of CoCL2 6H2O, the concentration >=0.040mol/L of urea, concentration >=the 0.008mol/L of ammonium fluoride, the volume >=25mL of redistilled water.
7. the preparation method of the wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material according to any one of claim 1-6, it is characterized in that, in step (3), nine water cure sodium concentration in mixed liquor is 0.01-0.03mol/L.
8. a wire nickel cobalt oxide nickel cobalt sulfide heterostructure composite material, is characterized in that, with nickel cobalt oxide nano wire for skeleton, utilize anion exchange method, by nickel cobalt oxide nano wire, by the etching of sulphion, be converted into nickel cobalt oxide@nickel cobalt sulfide nanometer linear.
9. wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material as claimed in claim 8, is characterized in that, adopts the method described in claim 1-7 to prepare.
10. the purposes of wire nickel cobalt oxide@nickel cobalt sulfide heterostructure composite material as described in claim 8 or 9, is characterized in that, as the electrode material of ultracapacitor.
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