CN106158405A - A kind of nickel hydroxide/graphene nanocomposite material and preparation method thereof, electrode of super capacitor and ultracapacitor - Google Patents
A kind of nickel hydroxide/graphene nanocomposite material and preparation method thereof, electrode of super capacitor and ultracapacitor Download PDFInfo
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- CN106158405A CN106158405A CN201610768005.8A CN201610768005A CN106158405A CN 106158405 A CN106158405 A CN 106158405A CN 201610768005 A CN201610768005 A CN 201610768005A CN 106158405 A CN106158405 A CN 106158405A
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- nickel hydroxide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 title claims abstract description 50
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title claims abstract description 46
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000003990 capacitor Substances 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 230000012010 growth Effects 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- 239000010439 graphite Substances 0.000 claims description 15
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 13
- 229930003268 Vitamin C Natural products 0.000 claims description 13
- 235000019154 vitamin C Nutrition 0.000 claims description 13
- 239000011718 vitamin C Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 150000002815 nickel Chemical class 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 238000004062 sedimentation Methods 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 206010013786 Dry skin Diseases 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 6
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 6
- 229940038773 trisodium citrate Drugs 0.000 claims description 6
- 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 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 abstract description 6
- 150000003624 transition metals Chemical class 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000002079 cooperative effect Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- -1 hydrogen Nickel oxide Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 244000061458 Solanum melongena Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009647 facial growth Effects 0.000 description 1
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- 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 OR LIGHT-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 OR LIGHT-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
Abstract
The invention discloses a kind of nickel hydroxide/graphene nanocomposite material and preparation method thereof, electrode of super capacitor and ultracapacitor, composite is made up of base material Graphene and the nickel hydroxide nano piece becoming at graphenic surface growth in situ, and composite is integrally in three-dimensional porous structure.The present invention at the graphenic surface carrying transition metal hydroxide with high-specific surface area and satisfactory electrical conductivity, prepares graphene-based composite by way of compound.Cooperative effect between each component of composite can make each component maximize favourable factors and minimize unfavourable ones mutually: in combination with the high specific capacitance characteristic of the high cycle life of electric double layer capacitance, high power density, high stability and fake capacitance, thus improves the combination property of ultracapacitor.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, be specifically related to a kind of nickel hydroxide/graphene nano composite wood
Material and preparation method thereof, electrode of super capacitor and ultracapacitor, nano composite material is by Graphene and at Graphene table
Face growth in situ nickel hydroxide nano piece is constituted, and hydroxide flake nickel/Graphene is self-assembled into three-dimensional porous structure.
Background technology
Ultracapacitor is also referred to as electrochemical capacitor, and has that the charging interval is short, length in service life, temperature characterisitic
Good, security height, the saving feature such as the energy and environmental protection.Ultracapacitor has higher power density and than secondary electricity because of it
The longer cycle life of pond, conventional electrostatic and electrolytic capacitor, causes sizable concern in the past few decades.Electrode
Material is the key of ultracapacitor performance boost, is also the factor determining ultracapacitor cost height.Ultracapacitor is pressed
Energy storage mechnism can be divided into double layer capacitor and fake capacitance capacitor.Material with carbon element is commonly applied to double layer capacitor, burning
Thing and conducting polymer are commonly applied to fake capacitance capacitor.
Graphene, because of its good crystalline structure, has higher electronic conductivity in surface region.Graphene have excellent
Remain able to while good electric conductivity and thermal conductivity maintain extra specific surface area.Therefore, once there is prophesy Graphene at electric double layer
Capacitor has broad application prospects.Yet with the Van der Waals force between Graphene adjacent sheet, Graphene is easily reunited, and makes stone
The active surface area of ink alkene reduces, thus causes losing a large amount of electric capacity.In order to improve the utilization rate of Graphene specific surface, improve stone
The chemical property of ink alkene, may utilize the defect that surface produces in Graphene preparation process and group, repaiies Graphene
Decorations, introduce metal hydroxides nano particle, thus hinder Graphene to reunite, and improve the utilization rate of Graphene.
Transition metal hydroxide is applied in ultracapacitor as electrode material, has higher than electric capacity, cheap, ring
The advantages such as guarantor, but transition metal hydroxide electric conductivity difference is its fatal defects applied in electricity device, limits it
Application on ultracapacitor.
Content of the invention
In view of prior art exists above-mentioned deficiency, the technical problem to be solved be to provide a kind of nickel hydroxide/
Graphene nanocomposite material and preparation method thereof, electrode of super capacitor and ultracapacitor.The present invention utilizes hydro-thermal legal system
Obtain three-dimensional porous nickel hydroxide/graphene nanocomposite material.The nickel hydroxide of the present invention/graphene nanocomposite material is made
For electrode material for super capacitor, effectively increase the performance of ultracapacitor.Nickel hydroxide/graphene nanocomposite material
Preparation method technique is simple, environmental protection, low cost.Nickel hydroxide/the graphene nanocomposite material of preparation in the form of sheets, and hydrogen
Nickel oxide nano piece is at graphenic surface growth in situ.
The technical solution used in the present invention is:
A kind of nickel hydroxide/graphene nanocomposite material, by base material Graphene and at graphenic surface growth in situ
The nickel hydroxide nano piece composition becoming, composite is integrally in three-dimensional porous structure.
A kind of preparation method of nickel hydroxide/graphene nanocomposite material, step includes:
1), disperse graphite oxide in deionized water, ultrasonically treated obtain graphene oxide solution ie in solution A.
2), by prepared nickel salt aqueous solution soluble in water for nickel salt, then nickel salt aqueous solution is joined in solution A, ultrasonic place
Reason obtains solution B；
3), by obtained solution soluble in water to vitamin C or trisodium citrate, then by molten to vitamin C or trisodium citrate
Liquid adds in solution B, ultrasonically treated obtains solution C；Preferably add vitamin c solution in solution B, ultrasonically treated obtain solution
C；
4), by obtained solution soluble in water to urea or hexa, then by urea liquid or hexa
Solution adds in solution C, ultrasonically treated obtains solution D；Preferably will after add urea liquid in solution C, ultrasonically treated obtain
Solution D；
5), solution D is transferred to reactor react 8～24 hours at 90～240 DEG C, preferably at 120～180 DEG C
React 10～18 hours；
6), product washing, obtains nickel hydroxide/graphene nanocomposite material after being dried.
Described step 1) graphite oxide prepared by improved Hummers method, and concrete preparation method is: weigh 5.0g stone respectively
Ink and 3.75g NaNO3Put in the beaker of 1L, machinery strong stirring, it is slowly added to the concentrated sulfuric acid of 150mL, stir 0.5 hour,
It is slow added into the KMnO of 20g4, within 0.5 hour, add, after continuing stirring 20 hours, reactant viscosity increases, and stops stirring,
To starchiness aubergine material.It after placing 5 days, is respectively added slowly to 500mL deionized water and 30mL H2O2, now solution colour
Become obvious glassy yellow, after solution fully reacts, centrifugal, washing, obtain graphene oxide.
Described step 1) in the concentration of graphene oxide solution be 0.05～1.0mg/mL, preferably 0.1～0.8mg/mL；Super
The sound time is 30～60 minutes, and in Ultrasound Instrument, the temperature of water is 5～50 DEG C；
Described step 2) in nickel salt selected from nickel chloride, nickel nitrate, one or more in nickel acetate, nickel salt concentration is 0.04
～0.6mol/L, preferably 0.1～0.4mol/L；Ultrasonic time is 15～60 minutes, and in Ultrasound Instrument, the temperature of water is 5～50 DEG C；
Described step 3) in the concentration of vitamin C or citric acid three sodium solution be 0.14～0.85mol/L, preferably 0.2～
0.6mol/L；Ultrasonic time is 15～60 minutes；In Ultrasound Instrument, the temperature of water is 5～50 DEG C；Step 3) in also can use dimension
Raw element C and the mixed solution of trisodium citrate, in mixed solution the total concentration of vitamin C and trisodium citrate be 0.14～
0.85mol/L, preferably 0.2～0.6mol/L；
Described step 4) in urea or hexa solution concentration be 0.16mol/L～1.8mol/L, preferably 0.4～
1.6mol/L；Ultrasonic time is 15～60 minutes；In Ultrasound Instrument, the temperature of water is 5～50 DEG C；Step 4) in can make urea and
The mixed solution of hexa, in mixed solution, the total concentration of urea and hexa is 0.16～1.8mol/L,
Preferably 0.4～1.6mol/L；
Described step 6) in washing for respectively with deionized water, ethanol sedimentation washing, 60 DEG C of dryings, sedimentation washing；
Described graphene oxide solution, nickel salt aqueous solution, vitamin C or citric acid three sodium solution, urea or hexa-methylene
The volume ratio of four amine aqueous solutions is 20:4:3:3.
A kind of electrode of super capacitor, is made up of nickel hydroxide/graphene nanocomposite material；
A kind of ultracapacitor, by the electrode of super capacitor including that nickel hydroxide/graphene nanocomposite material is made
Make.
The mechanism of the present invention is: the functional groups of nickel ion and surface of graphene oxide, urea divides under the high temperature conditions
A large amount of OH is produced after solution, hydrolysis-, OH-Be combined formation nickel hydroxide again with nickel ion, i.e. nickel hydroxide is at graphenic surface in situ
Growth, forms the nano combined material of the nickel hydroxide nano piece becoming with Graphene as base material and at graphenic surface growth in situ
Material.
The present invention by way of compound at the graphenic surface load transitions with high-specific surface area and satisfactory electrical conductivity
Metal hydroxides, prepares graphene-based composite.Cooperative effect between each component of composite can make each component mutual
Maximize favourable factors and minimize unfavourable ones: in combination with the height of the high cycle life of electric double layer capacitance, high power density, high stability and fake capacitance than electricity
Hold characteristic, thus improve the combination property of ultracapacitor.In graphene-based composite, at transition metal hydroxide electricity
Extremely middle introducing high conductivity Graphene may increase its electric conductivity；And if graphenic surface is modified by transition metal hydroxide
(load), then Graphene can be prevented from again being piled into sheet, and this can make it be polymerized minimum, and electrochemical contact area is maximum
Change.For this point, the Graphene of synthesis/transition metal hydroxide nano composite material can use for reference the advantage of the other side,
Thus two electrode material performances improve jointly.Improve the utilization rate of fake capacitance electrode material in this way, improve compound
The performance of material.
The present invention compared with prior art has the advantage that
(1) nickel hydroxide/graphene nanocomposite material obtained by integrally in three-dimensional porous shape, nickel hydroxide nano piece
Directly at graphenic surface growth in situ；
(2) nickel hydroxide nano piece can stop the heavily accumulation of Graphene at graphenic surface growth in situ, improves stone
The specific surface area utilization rate of ink alkene；
(3) nickel hydroxide nano piece can improve the conductance of nickel hydroxide at graphenic surface growth in situ, Graphene,
Thus improve its chemical property；
(4) preparation method of the nickel hydroxide/graphene nanocomposite material of the present invention is simple, gentle, environmental protection and
Low cost and other advantages.
Brief description
Fig. 1 is the SEM figure of the nickel hydroxide/graphene nanocomposite material of embodiment 1 preparation.
Fig. 2 is the XRD of the nickel hydroxide/graphene nanocomposite material of embodiment 2 preparation.
Fig. 3 is the SEM figure of the nickel hydroxide/graphene nanocomposite material of embodiment 2 preparation.
Fig. 4 is the SEM figure of the nickel hydroxide/graphene nanocomposite material of embodiment 3 preparation.
Fig. 5 is the SEM figure of the nickel hydroxide/graphene nanocomposite material of embodiment 4 preparation.
Fig. 6 is the SEM figure of the nickel hydroxide/graphene nanocomposite material of embodiment 5 preparation.
Fig. 7 is the TEM figure of the nickel hydroxide/graphene nanocomposite material of embodiment 5 preparation.
Fig. 8 is circulation under 0.5A/g current density for the nickel hydroxide/graphene nanocomposite material of embodiment 5 preparation
Stability test figure.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further detailed explanation.But embodiments of the present invention are not limited to this.
Embodiment 1
The preparation of graphite oxide: weigh 5.0g graphite and 3.75g NaNO respectively3Putting in the beaker of 1L, machinery strength is stirred
Mix, be slowly added to the concentrated sulfuric acid of 150mL, stir 0.5 hour, be slow added into the KMnO of 20g4, within 0.5 hour, add, continue to stir
After mixing 20 hours, reactant viscosity increases, and stops stirring, obtains starchiness aubergine material.After placing 5 days, slowly add respectively
Enter 500mL deionized water and 30mLH2O2, now solution colour becomes obvious glassy yellow, after solution fully reacts, from
The heart, washing, obtain graphite oxide.
Taking 5.0mg graphite oxide, being dispersed in 100mL deionized water, within ultrasonic 1 hour, obtain solution A, control water temperature is 5
～40 DEG C, the present embodiment water temperature is 25 DEG C.Weigh 0.6g Nickel dichloride hexahydrate to be dissolved in 20mL deionized water, add after stirring
Enter in solution A, within ultrasonic 30 minutes, obtain solution B.Take 0.5g vitamin C to be dissolved in 15mL deionized water, be stirring evenly and then adding into
In solution B, within ultrasonic 30 minutes, obtain solution C.Take 0.3g urea to be dissolved in 15mL deionized water, be stirring evenly and then adding into solution C
In, within ultrasonic 20 minutes, solution obtains solution D.Pouring solution D in the polytetrafluoroethylene (PTFE) reactor of 200mL, 140 DEG C of reactions 24 are little
When.
Product is washed 4 times by deionized water and ethanol sedimentation respectively, and 30 DEG C of dryings 12 hours, obtains hydroxide
Nickel/graphene nanocomposite material.
Embodiment 2
The preparation method of graphite oxide is with embodiment 1.Take 10.0mg graphite oxide, be dispersed in 100mL deionized water, super
Sound obtains solution A for 1 hour, and control water temperature is at 5～40 DEG C, and the present embodiment water temperature is 30 DEG C.Weigh 1.2g Nickel dichloride hexahydrate molten
It in 20mL deionized water, is stirring evenly and then adding in solution A, within ultrasonic 30 minutes, obtain solution B.Take 1.0g vitamin C to be dissolved in
It in 15mL deionized water, is stirring evenly and then adding in solution B, within ultrasonic 30 minutes, obtain solution C.Take 0.6g urea and be dissolved in 15mL
In ionized water, being stirring evenly and then adding in solution C, within ultrasonic 20 minutes, solution obtains solution D.Solution D is poured into poly-the four of 200mL
In PVF reactor, 120 DEG C are reacted 24 hours.
Product is washed 3 times by deionized water and ethanol sedimentation respectively, and 60 DEG C of dryings 10 hours, obtains hydroxide
Nickel/graphene nanocomposite material.
Embodiment 3
The preparation method of graphite oxide is with embodiment 1.Take 20.0mg graphite oxide, be dispersed in 100mL deionized water, super
Sound obtains solution A for 1 hour, and control water temperature is at 5～40 DEG C, and the present embodiment water temperature is 30 DEG C.Weigh 1.6g Nickel dichloride hexahydrate molten
It in 20mL deionized water, is stirring evenly and then adding in solution A, within ultrasonic 30 minutes, obtain solution B.Take 1.0g vitamin C to be dissolved in
It in 15mL deionized water, is stirring evenly and then adding in solution B, within ultrasonic 30 minutes, obtain solution C.Take 0.8g urea and be dissolved in 15mL
In ionized water, being stirring evenly and then adding in solution C, within ultrasonic 20 minutes, solution obtains solution D.Solution D is poured into poly-the four of 200mL
In PVF reactor, 140 DEG C are reacted 12 hours.
By product respectively with deionized water and ethanol sedimentation washing 3 times, and 80 DEG C of dryings 6 hours, obtain nickel hydroxide/
Graphene nanocomposite material.
Embodiment 4
The preparation method of graphite oxide is with embodiment 1.Take 30.0mg graphite oxide, be dispersed in 100mL deionized water, super
Sound obtains solution A for 1 hour, and control water temperature is at 5～40 DEG C, and the present embodiment water temperature is 30 DEG C.Weigh 2.0g nickel nitrate and be dissolved in 20mL
It in deionized water, is stirring evenly and then adding in solution A, within ultrasonic 30 minutes, obtain solution B.Take 2.0g vitamin C and be dissolved in 15mL
It in ionized water, is stirring evenly and then adding in solution B, within ultrasonic 30 minutes, obtain solution C.Take 1.0g urea and be dissolved in 15mL deionized water
In, it is stirring evenly and then adding in solution C, within ultrasonic 20 minutes, solution obtains solution D.Solution D is poured into the polytetrafluoroethylene (PTFE) of 200mL
In reactor, 160 DEG C are reacted 18 hours.
Product is washed 5 times by deionized water and ethanol sedimentation respectively, and 100 DEG C of dryings 4 hours, obtains hydroxide
Nickel/graphene nanocomposite material.
Embodiment 5
The preparation method of graphite oxide is with embodiment 1.Take 50.0mg graphite oxide, be dispersed in 100mL deionized water, super
Sound obtains solution A for 1 hour, and control water temperature is at 5～40 DEG C, and the present embodiment water temperature is 30 DEG C.Weigh 3.0g Nickel dichloride hexahydrate molten
It in 20mL deionized water, is stirring evenly and then adding in solution A, within ultrasonic 30 minutes, obtain solution B.Take 3.0g vitamin C to be dissolved in
It in 15mL deionized water, is stirring evenly and then adding in solution B, within ultrasonic 30 minutes, obtain solution C.Take 2.0g hexa molten
In 15mL deionized water, being stirring evenly and then adding in solution C, within ultrasonic 20 minutes, solution obtains solution D.Solution D is poured into
In the polytetrafluoroethylene (PTFE) reactor of 200mL, 200 DEG C are reacted 10 hours.
Product is washed 3 times by deionized water and ethanol sedimentation respectively, and 120 DEG C of dryings 3 hours, obtains hydroxide
Nickel/graphene nanocomposite material.
Using example 5 gained end product nickel hydroxide/graphene nanocomposite material as the electrode material of ultracapacitor
Material, uses composite, the mass ratio of acetylene black and PTFE is 85:10:5, is modulated into homogeneous solution with ethanol for solvent, by molten
Liquid is coated in 1cm2Nickel foam on, in vacuum drying chamber 60 DEG C dry 12 hours.Dry after completing to scribbling composite
Nickel foam carries out compressing tablet process.Three-electrode system is utilized to carry out electrochemical property test to material, at ultracapacitor at 0.5A/
Cyclical stability test figure under g current density is as shown in Figure 8.From accompanying drawing 8, the cyclical stability of ultracapacitor is good
Good, after circulating 1000 times, still retain more than the 90% of initial capacitance.
Claims (10)
1. nickel hydroxide/graphene nanocomposite material, by base material Graphene and in the growth of graphene film surface in situ
The nickel hydroxide nano piece composition becoming, composite is integrally in three-dimensional porous structure.
2. a preparation method for nickel hydroxide/graphene nanocomposite material, step includes:
1), disperse graphite oxide in deionized water, ultrasonically treated obtain graphene oxide solution ie in solution A.
2), by prepared nickel salt aqueous solution soluble in water for nickel salt, then nickel salt aqueous solution is joined in solution A, ultrasonically treated
To solution B；
3), by obtained solution soluble in water to vitamin C or trisodium citrate, then vitamin C or citric acid three sodium solution are added
Enter in solution B, ultrasonically treated obtain solution C；Preferably add vitamin c solution in solution B, ultrasonically treated obtain solution C；
4), by obtained solution soluble in water to urea or hexa, then by urea liquid or hexa solution
Add in solution C, ultrasonically treated obtain solution D；Preferably will after add urea liquid in solution C, ultrasonically treated obtain solution
D；
5), solution D is transferred to reactor reacts 8～24 hours at 90～240 DEG C, preferably react at 120～180 DEG C
10～18 hours；
6), product washing, obtains nickel hydroxide/graphene nanocomposite material after being dried.
3. preparation method as claimed in claim 2, it is characterised in that: described step 1) in the concentration of graphene oxide solution be
0.05～1.0mg/mL, preferably 0.1～0.8mg/mL；Ultrasonic time is 30～60 minutes, and in Ultrasound Instrument, the temperature of water is 5～50
℃。
4. preparation method as claimed in claim 2, it is characterised in that: in described step 2 nickel salt selected from nickel chloride, nickel nitrate,
One or more in nickel acetate, nickel salt concentration is 0.04～0.6mol/L, preferably 0.1～0.4mol/L；Ultrasonic time is 15
～60 minutes, in Ultrasound Instrument, the temperature of water was 5～50 DEG C.
5. preparation method as claimed in claim 2, it is characterised in that: described step 3) in vitamin C or trisodium citrate molten
The concentration of liquid is 0.14～0.85mol/L, preferably 0.2～0.6mol/L；Ultrasonic time is 15～60 minutes；Water in Ultrasound Instrument
Temperature is 5～50 DEG C.
6. preparation method as claimed in claim 2, it is characterised in that: described step 4) in urea or hexa solution
Concentration is 0.16～1.8mol/L, preferably 0.4～1.6mol/L；Ultrasonic time is 15～60 minutes；The temperature of water in Ultrasound Instrument
It is 5～50 DEG C.
7. preparation method as claimed in claim 2, it is characterised in that: described step 6) in washing for respectively with deionized water,
Ethanol sedimentation washing, 30～120 DEG C of dryings 3～12 hours.
8. preparation method as claimed in claim 2, it is characterised in that: described graphene oxide solution, nickel salt aqueous solution, dimension are raw
The volume ratio of element C or citric acid three sodium solution, urea or hexa solution is 20:4:3:3.
9. an electrode of super capacitor, is made up of nickel hydroxide/graphene nanocomposite material.
10. a ultracapacitor, by the electrode of super capacitor system including that nickel hydroxide/graphene nanocomposite material is made
Become.
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| CN110085440A (en) * | 2019-04-23 | 2019-08-02 | 中国计量大学 | A kind of nickel hydroxide/redox graphene electrode material preparation method |
| CN111348689A (en) * | 2020-02-12 | 2020-06-30 | 杭州电子科技大学 | A kind of Ni (OH)2Graphene composite material and preparation method thereof |
| CN111790387A (en) * | 2020-08-07 | 2020-10-20 | 福州大学 | Transition metal hydroxide-graphene composite material for efficient photocatalytic reduction of carbon dioxide and preparation method and application thereof |
| CN111790387B (en) * | 2020-08-07 | 2021-11-26 | 福州大学 | Transition metal hydroxide-graphene composite material for efficient photocatalytic reduction of carbon dioxide and preparation method and application thereof |
| CN113371752A (en) * | 2021-05-31 | 2021-09-10 | 江汉大学 | Ni (OH) applied to super capacitor2/KCu7S4Composite electrode material and preparation method thereof |
| CN113371752B (en) * | 2021-05-31 | 2022-11-22 | 江汉大学 | Ni (OH) applied to super capacitor 2 /CuO@Cu 7 S 4 Composite electrode material and preparation method thereof |
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