CN106910647A - Compound cobalt acid nickel nano-wire array material of graphene aerogel and preparation method thereof - Google Patents
Compound cobalt acid nickel nano-wire array material of graphene aerogel and preparation method thereof Download PDFInfo
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- CN106910647A CN106910647A CN201710272732.XA CN201710272732A CN106910647A CN 106910647 A CN106910647 A CN 106910647A CN 201710272732 A CN201710272732 A CN 201710272732A CN 106910647 A CN106910647 A CN 106910647A
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- graphene aerogel
- cobalt acid
- acid nickel
- wire array
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 102
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 92
- 239000010941 cobalt Substances 0.000 title claims abstract description 92
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002253 acid Substances 0.000 title claims abstract description 90
- 239000004964 aerogel Substances 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 57
- 150000001875 compounds Chemical class 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 15
- 239000002070 nanowire Substances 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 238000003491 array Methods 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- -1 wherein Chemical class 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
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- General Physics & Mathematics (AREA)
- Composite Materials (AREA)
Abstract
The present invention relates to compound cobalt acid nickel nano-wire array material of a kind of graphene aerogel and preparation method thereof.Its technical scheme is：By graphene oxide solution, hydro-thermal reaction, drying in reactor, obtain graphene aerogel.By Nickel dichloride hexahydrate: cobalt chloride hexahydrate: the mol ratio of urea is 1: 2:（7~10）Concentration with Nickel dichloride hexahydrate is 0.016 ~ 0.1mol/L, and Nickel dichloride hexahydrate, cobalt chloride hexahydrate and urea are dissolved in deionized water, is stirred, and obtains mixed solution.By graphene aerogel: the mass ratio of the Nickel dichloride hexahydrate in mixed solution is 1:（2~4）Graphene aerogel is put into mixed solution, hydro-thermal reaction, dried, obtain presoma.Presoma is incubated 1.5 ~ 3h at 300 ~ 400 DEG C, the compound cobalt acid nickel nano-wire array material of graphene aerogel is obtained.Present invention process is simple, environment-friendly and can realize industrialized production, and prepared product specific capacity is high, good rate capability and cyclical stability are excellent.
Description
Technical field
The invention belongs to cobalt acid nickel nano-wire array technical field of composite materials.Specifically related to a kind of graphene aerogel is answered
Close cobalt acid nickel nano-wire array material and preparation method thereof.
Background technology
Ultracapacitor is a kind of new type of energy storage device between traditional capacitor and battery, it is considered to be most had
The reproducible of development prospect, the energy conversion of cleaning and storage device, with specific energy is high, operating temperature range wide, use
Long lifespan, good cycle, power density be big and the advantages of environmental protection, be widely used in electronic product, electric automobile industry,
The field such as Aero-Space and redundant electrical power.At present, the research of electrode material for super capacitor mainly includes carbon material, metal oxygen
Compound and conducting polymer, wherein, metal oxide is of much attention with its specific capacity high.
It is cobalt acid nickel wide material sources, cheap and environmentally friendly, as a kind of transiting metal oxidation of polyhybird valence state
Thing, with than NiO and Co3O4Electrical conductivity higher and electrochemical reaction activity, the suitable electrode material that exactly we find.
But the intrinsic low native electronic electrical conductivity of cobalt acid nickel has still had a strong impact on its performance, particularly high rate performance and circulation is steady
Qualitative energy, and then limit application of the cobalt acid nickel in electrochemical energy storage.Although cobalt acid nickel and carbon fiber have been developed at present
Or the compound method of modifying of Graphene, though the chemical property of lifting cobalt acid nickel to a certain extent, carbon fiber loaded easy
The reunion of cobalt acid nickel is formed so as to reduce active specific surface, and graphene sheet layer easily stacks form sheet during the course of the reaction,
These problems remain unchanged and limit the performance of cobalt acid nickel material, it is difficult to meet property higher and higher to electrode material for super capacitor
Can require.
The content of the invention
It is contemplated that overcoming the deficiencies in the prior art, it is therefore intended that provide a kind of process is simple, easy to operate, environment friendly
The preparation method of the compound cobalt acid nickel nano-wire array material of graphene aerogel good and that industrialized production can be realized；Use the method
The compound cobalt acid nickel nano-wire array material specific capacity of the graphene aerogel of preparation is high, good rate capability and cyclical stability are excellent
It is different.
To achieve the above object, the present invention is adopted the following technical scheme that：
（1）It is 2 ~ 2.5kg/m by concentration3Graphene oxide solution be placed in reactor, the hydro-thermal under the conditions of 145 ~ 155 DEG C
2 ~ 3h of reaction, natural cooling, freeze-drying is obtained graphene aerogel.
（2）By Nickel dichloride hexahydrate: cobalt chloride hexahydrate: the mol ratio of urea is 1: 2:（7~10）Dispensing, then by six water
Close nickel chloride concentration be 0.016 ~ 0.1mol/L, by the Nickel dichloride hexahydrate, cobalt chloride hexahydrate and urea be dissolved in from
In sub- water, stirring, ultrasonic disperse obtains mixed solution.
（3）By the graphene aerogel: the mass ratio of the Nickel dichloride hexahydrate in the mixed solution is 1:（2~4）,
The graphene aerogel is put into the mixed solution, 20 ~ 24h of hydro-thermal reaction under the conditions of 90 ~ 95 DEG C, natural cooling,
Washing, freeze-drying obtains presoma.
（4）The presoma is placed in tube-type atmosphere furnace, 300 ~ 400 DEG C, insulation are warming up to 1 ~ 2 DEG C/min speed
1.5 ~ 3h, cooling is obtained the compound cobalt acid nickel nano-wire array material of graphene aerogel.
The cobalt acid nickel nano wire of the compound cobalt acid nickel nano-wire array material of the graphene aerogel and three-dimensional macropore airsetting
Graphene in glue is combined, and forms compact arranged nano-wire array, and the cobalt acid nickel nano wire of load is loose structure, is formed
The compound cobalt acid nickel nano-wire array material of aeroge macropore nested graphene aerogel mesoporous with nano wire.
It is pure that the Nickel dichloride hexahydrate, cobalt chloride hexahydrate and urea are analysis.
The washing is first to be washed 3 ~ 5 times with ethanol, then is washed with deionized water 3 ~ 5 times, then soaks 8 ~ 12 with deionized water
Hour, then be washed with deionized water 3 ~ 5 times.
Due to using above-mentioned technical proposal, having the beneficial effect that relative to prior art of the invention：
（1）The present invention first through simple hydro-thermal reaction be obtain graphene aerogel, then by the graphene aerogel with it is prefabricated
Mixed solution hydro-thermal reaction, the then compound cobalt acid nickel nano-wire array material of thermally treated prepared graphene aerogel, therefore work
Skill is simple.
（2）The waste liquid environmental pollution discharged after the present invention discharges without toxic gas during the course of the reaction, and reaction terminates
It is small, environmental protection.The cobalt source and nickel source for preparing cobalt acid nickel are cheap, and equipment needed for production process is simple, low production cost.
（3）Cobalt acid nickel nano wire in the compound cobalt acid nickel nano-wire array material of graphene aerogel prepared by the present invention is tight
Solid matter is listed on graphene sheet layer, and specific surface area is high；Three-dimensional grapheme aeroge forms space structure, can be effectively reduced electrification
The reunion of graphene sheet layer is stacked during, and electric conductivity high can significantly improve the conduction of electronics, lifting cobalt acid nickel in addition
Specific capacity, multiplying power and cycle performance.
（4）The cobalt acid nickel nano wire and three of the compound cobalt acid nickel nano-wire array material of graphene aerogel prepared by the present invention
Graphene in dimension macropore aeroge is combined, and forms compact arranged nano-wire array, and the cobalt acid nickel nano wire of load is many
Pore structure, forms the compound cobalt acid nickel nano-wire array material of aeroge macropore nested graphene aerogel mesoporous with nano wire.
Three-dimensional macropore therein can accelerate the infiltration of electrolyte with mesoporous nested loose structure, increase active material and connect with electrolyte
Tactile active surface area, while ion transmission channel is shortened, so that the further specific capacity of lifting cobalt acid nickel, multiplying power and circulation
Performance.
（5）The compound cobalt acid nickel nano-wire array material of graphene aerogel prepared by the present invention is after testing：Graphene airsetting
The aperture of glue is 50 ~ 200 μm, and cobalt acid nickel nano wire is evenly distributed on graphene sheet layer；The cobalt acid nickel nano wire of made product
It is loose structure, aperture is 3 ~ 15nm；Specific surface area is 50 ~ 90m2/g。
The compound cobalt acid nickel nano-wire array material of graphene aerogel prepared by the present invention is through electrochemical property test：It is made
Product is 1A g in current density-1Under the conditions of specific capacity be 1990 ~ 2200F g-1；It is 100A g in current density-1Under the conditions of
Specific capacity be 970 ~ 1000F g-1；It is 80A g in current density-1Under the conditions of specific capacity be 1100 ~ 1200F g-1, pass through
Capability value conservation rate is up to 80 ~ 88% after 10000 cyclic processes.
Therefore, the present invention has process is simple, easy to operate, environment-friendly and the characteristics of can realize industrialized production, institute
The compound cobalt acid nickel nano-wire array material specific capacity of the graphene aerogel of preparation is high, good rate capability and cyclical stability are excellent
It is different.
Brief description of the drawings
Fig. 1 is a kind of SEM figures of the compound cobalt acid nickel nano-wire array material of graphene aerogel prepared by the present invention；
Fig. 2 is the XRD of the compound cobalt acid nickel nano-wire array material of graphene aerogel shown in Fig. 1；
Fig. 3 is the TEM figures of the compound cobalt acid nickel nano-wire array material of graphene aerogel shown in Fig. 1.
Specific embodiment
The present invention is described further below in conjunction with the drawings and specific embodiments, not to the claims in the present invention model
The limitation enclosed.
In this specific embodiment：
In the cobalt acid nickel nano wire and three-dimensional macropore aeroge of the compound cobalt acid nickel nano-wire array material of the graphene aerogel
Graphene be combined, form compact arranged nano-wire array, the cobalt acid nickel nano wire of load is loose structure, forms airsetting
The compound cobalt acid nickel nano-wire array material of glue macropore nested graphene aerogel mesoporous with nano wire.
It is pure that the Nickel dichloride hexahydrate, cobalt chloride hexahydrate and urea are analysis.
The washing is first to be washed 3 ~ 5 times with ethanol, then is washed with deionized water 3 ~ 5 times, then soaks 8 ~ 12 with deionized water
Hour, then be washed with deionized water 3 ~ 5 times.
Repeated no more in embodiment.
Embodiment 1
Compound cobalt acid nickel nano-wire array material of a kind of graphene aerogel and preparation method thereof.Preparation method described in the present embodiment
Comprise the concrete steps that：
（1）It is 2 ~ 2.5kg/m by concentration3Graphene oxide solution be placed in reactor, the hydro-thermal under the conditions of 145 ~ 155 DEG C
2 ~ 3h of reaction, natural cooling, freeze-drying is obtained graphene aerogel.
（2）By Nickel dichloride hexahydrate: cobalt chloride hexahydrate: the mol ratio of urea is 1: 2:（7~8）Dispensing, then by six hydrations
The concentration of nickel chloride is 0.016 ~ 0.04mol/L, and the Nickel dichloride hexahydrate, cobalt chloride hexahydrate and urea are dissolved in into deionization
In water, stirring, ultrasonic disperse obtains mixed solution.
（3）By the graphene aerogel: the mass ratio of the Nickel dichloride hexahydrate in the mixed solution is 1:（2~3）,
The graphene aerogel is put into the mixed solution, 20 ~ 24h of hydro-thermal reaction under the conditions of 90 ~ 95 DEG C, natural cooling,
Washing, freeze-drying obtains presoma.
（4）The presoma is placed in tube-type atmosphere furnace, 300 ~ 330 DEG C, insulation are warming up to 1 ~ 2 DEG C/min speed
2.5 ~ 3h, cooling is obtained the compound cobalt acid nickel nano-wire array material of graphene aerogel.
Fig. 1 is a kind of SEM figures of the compound cobalt acid nickel nano-wire array material of graphene aerogel manufactured in the present embodiment；Figure
2 is the XRD of the compound cobalt acid nickel nano-wire array material of graphene aerogel shown in Fig. 1；Fig. 3 is Graphene airsetting shown in Fig. 1
The TEM figures of the compound cobalt acid nickel nano-wire array material of glue.As seen from Figure 1, in its product cobalt acid nickel nano-wire array according to
Attached thin graphene grows and is cross-linked, and graphene sheet layer forms the space structure of three-dimensional interconnection, the hole of graphene aerogel
Footpath is 130 ~ 200 μm, and cobalt acid nickel nano wire is evenly distributed on graphene sheet layer；As seen from Figure 2, its product is pure phase
NiCo2O4Material（PDF#20-0781）；As seen from Figure 3, the cobalt acid nickel nano wire of its product is loose structure, and aperture is 10
~15nm.Tested through BET, specific surface area is 50-70m2/g。
The compound cobalt acid nickel nano-wire array material of graphene aerogel manufactured in the present embodiment is through electrochemical property test：
Current density is 1A g-1Under the conditions of specific capacity be 1990 ~ 2080F g-1；It is 100A g in current density-1Under the conditions of specific volume
It is 970 ~ 985F g to measure-1；It is 80A g in current density-1Under the conditions of specific capacity be 1100 ~ 1150F g-1, by 10000 times
Capability value conservation rate is up to 84 ~ 88% after cyclic process.
Embodiment 2
Compound cobalt acid nickel nano-wire array material of a kind of graphene aerogel and preparation method thereof.Preparation method described in the present embodiment
Comprise the concrete steps that：
（1）It is 2 ~ 2.5kg/m by concentration3Graphene oxide solution be placed in reactor, the hydro-thermal under the conditions of 145 ~ 155 DEG C
2 ~ 3h of reaction, natural cooling, freeze-drying is obtained graphene aerogel.
（2）By Nickel dichloride hexahydrate: cobalt chloride hexahydrate: the mol ratio of urea is 1: 2:（8~9）Dispensing, then by six hydrations
The concentration of nickel chloride is 0.04 ~ 0.07mol/L, and the Nickel dichloride hexahydrate, cobalt chloride hexahydrate and urea are dissolved in into deionization
In water, stirring, ultrasonic disperse obtains mixed solution.
（3）By the graphene aerogel: the mass ratio of the Nickel dichloride hexahydrate in the mixed solution is 1:（2.5~
3.5）, the graphene aerogel is put into the mixed solution, 20 ~ 24h of hydro-thermal reaction under the conditions of 90 ~ 95 DEG C, it is natural
Cooling, washing, freeze-drying obtains presoma.
（4）The presoma is placed in tube-type atmosphere furnace, 330 ~ 370 DEG C are warming up to 1 ~ 2 DEG C/min speed, insulation 2 ~
2.5h, cooling is obtained the compound cobalt acid nickel nano-wire array material of graphene aerogel.
The compound cobalt acid nickel nano-wire array material of graphene aerogel manufactured in the present embodiment is after testing：Graphene aerogel
Aperture be 90 ~ 160 μm, cobalt acid nickel nano wire be evenly distributed on graphene sheet layer；Made product cobalt acid nickel nano wire be
Loose structure, aperture is 7 ~ 12nm；Specific surface area is 60 ~ 80m2/g。
The compound cobalt acid nickel nano-wire array material of graphene aerogel manufactured in the present embodiment is through electrochemical property test：
Current density is 1A g-1Under the conditions of specific capacity be 2050 ~ 2140F g-1；It is 100A g in current density-1Under the conditions of specific volume
It is 980 ~ 995F g to measure-1；It is 80A g in current density-1Under the conditions of specific capacity be 1130 ~ 1180F g-1, by 10000 times
Capability value conservation rate is up to 82 ~ 86% after cyclic process.
Embodiment 3
Compound cobalt acid nickel nano-wire array material of a kind of graphene aerogel and preparation method thereof.Preparation method described in the present embodiment
Comprise the concrete steps that：
（1）It is 2 ~ 2.5kg/m by concentration3Graphene oxide solution be placed in reactor, the hydro-thermal under the conditions of 145 ~ 155 DEG C
2 ~ 3h of reaction, natural cooling, freeze-drying is obtained graphene aerogel.
（2）By Nickel dichloride hexahydrate: cobalt chloride hexahydrate: the mol ratio of urea is 1: 2:（9~10）Dispensing, then by six water
The concentration for closing nickel chloride is 0.07 ~ 0.1mol/L, and the Nickel dichloride hexahydrate, cobalt chloride hexahydrate and urea are dissolved in into deionization
In water, stirring, ultrasonic disperse obtains mixed solution.
（3）By the graphene aerogel: the mass ratio of the Nickel dichloride hexahydrate in the mixed solution is 1:（3~4）,
The graphene aerogel is put into the mixed solution, 20 ~ 24h of hydro-thermal reaction under the conditions of 90 ~ 95 DEG C, natural cooling,
Washing, freeze-drying obtains presoma.
（4）The presoma is placed in tube-type atmosphere furnace, 370 ~ 400 DEG C, insulation are warming up to 1 ~ 2 DEG C/min speed
1.5 ~ 2h, cooling is obtained the compound cobalt acid nickel nano-wire array material of graphene aerogel.
The compound cobalt acid nickel nano-wire array material of graphene aerogel manufactured in the present embodiment is after testing：Graphene aerogel
Aperture be 50 ~ 120 μm, cobalt acid nickel nano wire be evenly distributed on graphene sheet layer；Made product cobalt acid nickel nano wire be
Loose structure, aperture is 3 ~ 8nm；Specific surface area is 70 ~ 90m2/g。
The compound cobalt acid nickel nano-wire array material of graphene aerogel manufactured in the present embodiment is through electrochemical property test：
Current density is 1A g-1Under the conditions of specific capacity be 2110 ~ 2200F g-1；It is 100A g in current density-1Under the conditions of specific volume
It is 985 ~ 1000F g to measure-1；It is 80A g in current density-1Under the conditions of specific capacity be 1150 ~ 1200F g-1, by 10000 times
Capability value conservation rate is up to 80 ~ 84% after cyclic process.
This specific embodiment has the beneficial effect that relative to prior art：
（1）This specific embodiment is first to obtain graphene aerogel through simple hydro-thermal reaction, then by the Graphene airsetting
Glue and prefabricated mixed solution hydro-thermal reaction, it is then thermally treated to obtain the compound cobalt acid nickel nano-wire array material of graphene aerogel
Material, therefore process is simple.
（2）The waste liquid pair discharged after this specific embodiment discharges without toxic gas during the course of the reaction, and reaction terminates
Environmental pollution is small, environmental protection.The cobalt source and nickel source for preparing cobalt acid nickel are cheap, and equipment needed for production process is simple, production
Low cost.
（3）Cobalt acid nickel in the compound cobalt acid nickel nano-wire array material of graphene aerogel prepared by this specific embodiment
Nano wire is arranged closely on graphene sheet layer, and specific surface area is high；Three-dimensional grapheme aeroge forms space structure, can be effectively
The reunion stacking of graphene sheet layer in electrochemical process is reduced, electric conductivity high can significantly improve the conduction of electronics in addition, carry
Rise specific capacity, multiplying power and the cycle performance of cobalt acid nickel.
（4）The cobalt acid nickel of the compound cobalt acid nickel nano-wire array material of graphene aerogel prepared by this specific embodiment is received
Rice noodles are combined with the Graphene in three-dimensional macropore aeroge, form compact arranged nano-wire array, and the cobalt acid nickel of load is received
Rice noodles are loose structure, form the compound cobalt acid nickel nanometer linear array of aeroge macropore nested graphene aerogel mesoporous with nano wire
Row material.Three-dimensional macropore therein can accelerate the infiltration of electrolyte with mesoporous nested loose structure, increase active material with
The active surface area of electrolyte contacts, while shorten ion transmission channel so that further the specific capacity of lifting cobalt acid nickel, times
Rate and cycle performance.
（5）The compound cobalt acid nickel nano-wire array material of graphene aerogel prepared by this specific embodiment is after testing：Stone
The aperture of black alkene aeroge is 50 ~ 200 μm, and cobalt acid nickel nano wire is evenly distributed on graphene sheet layer；The cobalt acid of made product
Nickel nano wire is loose structure, and aperture is 3 ~ 15nm；Specific surface area is 50 ~ 90m2/g。
The compound cobalt acid nickel nano-wire array material of graphene aerogel prepared by this specific embodiment is through chemical property
Test：Made product is 1A g in current density-1Under the conditions of specific capacity be 1990 ~ 2200F g-1；It is 100A in current density
g-1Under the conditions of specific capacity be 970 ~ 1000F g-1；It is 80A g in current density-1Under the conditions of specific capacity be 1100 ~ 1200F
g-1, by capability value conservation rate after 10000 cyclic processes up to 80 ~ 88%.
Therefore, this specific embodiment has process is simple, easy to operate, environment-friendly and can realize industrialized production
Feature, the compound cobalt acid nickel nano-wire array material specific capacity of prepared graphene aerogel is high, good rate capability and circulation are steady
It is qualitative excellent.
Claims (4)
1. a kind of graphene aerogel is combined the preparation method of cobalt acid nickel nano-wire array material, it is characterised in that the preparation side
The step of method is：
(1) it is 2~2.5kg/m by concentration3Graphene oxide solution be placed in reactor, the water under the conditions of 145~155 DEG C
2~3h of thermal response, natural cooling, freeze-drying is obtained graphene aerogel；
(2) by Nickel dichloride hexahydrate: cobalt chloride hexahydrate: the mol ratio of urea is 1: 2: (7~10) dispensing, then by six hydration chlorine
The concentration for changing nickel is 0.016~0.1mol/L, and the Nickel dichloride hexahydrate, cobalt chloride hexahydrate and urea are dissolved in into deionized water
In, stirring, ultrasonic disperse obtains mixed solution；
(3) by the graphene aerogel: the mass ratio of the Nickel dichloride hexahydrate in the mixed solution is 1: (2~4), by institute
State graphene aerogel to be put into the mixed solution, 20~24h of hydro-thermal reaction, natural cooling, wash under the conditions of 90~95 DEG C
Wash, freeze-drying obtains presoma；
(4) presoma is placed in tube-type atmosphere furnace, 300~400 DEG C, insulation 1.5 is warming up to 1~2 DEG C/min speed
~3h, cooling is obtained the compound cobalt acid nickel nano-wire array material of graphene aerogel；
In the cobalt acid nickel nano wire and three-dimensional macropore aeroge of the compound cobalt acid nickel nano-wire array material of the graphene aerogel
Graphene be combined, form compact arranged nano-wire array, the cobalt acid nickel nano wire of load is loose structure, forms airsetting
The compound cobalt acid nickel nano-wire array material of glue macropore nested graphene aerogel mesoporous with nano wire.
2. graphene aerogel according to claim 1 is combined the preparation method of cobalt acid nickel nano-wire array material, and it is special
Levy be the Nickel dichloride hexahydrate, cobalt chloride hexahydrate and urea be analysis it is pure.
3. graphene aerogel according to claim 1 is combined the preparation method of cobalt acid nickel nano-wire array material, and it is special
It is that the washing is first to be washed 3~5 times with ethanol to levy, then is washed with deionized water 3~5 times, then soaks 8~12 with deionized water
Hour, then be washed with deionized water 3~5 times.
4. a kind of graphene aerogel is combined cobalt acid nickel nano-wire array material, it is characterised in that the graphene aerogel is combined
Cobalt acid nickel nano-wire array material is that the compound cobalt acid nickel of the graphene aerogel according to any one of claims 1 to 3 is received
The compound cobalt acid nickel nano-wire array material of graphene aerogel prepared by the preparation method of nanowire arrays material.
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