CN106158405B - 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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- CN106158405B CN106158405B CN201610768005.8A CN201610768005A CN106158405B CN 106158405 B CN106158405 B CN 106158405B CN 201610768005 A CN201610768005 A CN 201610768005A CN 106158405 B CN106158405 B CN 106158405B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 86
- 239000000463 material Substances 0.000 title claims abstract description 48
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title claims abstract description 48
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000003990 capacitor Substances 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 126
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 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 29
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 23
- 239000004202 carbamide Substances 0.000 claims description 23
- 150000002815 nickel Chemical class 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 238000002604 ultrasonography Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 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
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 235000019154 vitamin C Nutrition 0.000 claims description 13
- 239000011718 vitamin C Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- 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 8
- 229940038773 trisodium citrate Drugs 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 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 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 238000001035 drying Methods 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
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 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
- 239000000203 mixture Substances 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
- 230000012010 growth Effects 0.000 abstract description 8
- 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
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 22
- 239000003643 water by type Substances 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 229930003231 vitamin Natural products 0.000 description 5
- 235000013343 vitamin Nutrition 0.000 description 5
- 239000011782 vitamin Substances 0.000 description 5
- 229940088594 vitamin Drugs 0.000 description 5
- 150000003722 vitamin derivatives Chemical class 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical class O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- -1 hydrogen Nickel oxide Chemical class 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
- 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 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
- 238000010586 diagram Methods 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
- 239000012467 final product Substances 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 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
-
- 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 ultracapacitors, composite material by base material graphene and on the surface of graphene growth in situ at nickel hydroxide nano piece form, composite material integrally be in three-dimensional porous structure.The present invention, in the graphene surface carrying transition metal hydroxide with high-specific surface area and satisfactory electrical conductivity, prepares graphene-based composite material by compound mode.Synergistic effect between composite material each component can make each component maximize favourable factors and minimize unfavourable ones mutually：In combination with the high specific capacitance characteristic of the high circulation service life of electric double layer capacitance, high power density, high stability and fake capacitance, to improve the comprehensive performance of ultracapacitor.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, and in particular to a kind of nickel hydroxide/graphene nano composite wood
Material and preparation method thereof, electrode of super capacitor and ultracapacitor, nanocomposite is by graphene and in 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 with the charging time is short, service life is long, temperature characterisitic
The features such as good, safe, energy saving and environmentally protective.Ultracapacitor has higher power density and than secondary electricity because of it
Pond, conventional electrostatic and the longer cycle life of electrolytic capacitor, cause sizable concern in the past few decades.Electrode
Material is the key that performance of the supercapacitor is promoted, and determines the factor of ultracapacitor cost height.Ultracapacitor is pressed
Energy storage mechnism can be divided into double layer capacitor and fake capacitance capacitor.Carbon material is commonly applied to double layer capacitor, metal oxidation
Object and conducting polymer are commonly applied to fake capacitance capacitor.
Graphene has higher electronic conductivity because of its good crystalline structure, in surface region.Graphene is with excellent
It remains able to maintain extra specific surface area while good electric conductivity and thermal conductivity.Therefore, once there is prophesy graphene in electric double layer
Have broad application prospects in capacitor.However due to the Van der Waals force between graphene adjacent sheet, graphene is easy to reunite, and makes stone
The active surface area of black alkene reduces, so as to cause a large amount of capacitances are lost.In order to improve the utilization rate of graphene specific surface, improve stone
The chemical property of black alkene repaiies graphene using the defect and group that surface generates in graphene preparation process
Decorations introduce metal hydroxides nano particle and improve the utilization rate of graphene to hinder graphene to reunite.
Transition metal hydroxide is applied as electrode material in ultracapacitor, there is that specific capacitance is high, cheap, ring
The advantages that guarantor, but transition metal hydroxide electric conductivity difference is the fatal defects that it is applied in electricity device, limits it
Application on ultracapacitor.
Invention content
In view of the prior art there are above-mentioned deficiency, technical problem to be solved by the invention is 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, the performance of ultracapacitor is effectively increased.Nickel hydroxide/graphene nanocomposite material
Preparation method is simple for process, environmentally protective, at low cost.Nickel hydroxide/graphene nanocomposite material of preparation in the form of sheets, and hydrogen
Nickel oxide nano piece growth in situ on the surface of graphene.
The technical solution adopted by the present invention is：
A kind of nickel hydroxide/graphene nanocomposite material, by base material graphene and growth in situ on the surface of graphene
At nickel hydroxide nano piece composition, composite material integrally be in three-dimensional porous structure.
A kind of preparation method of nickel hydroxide/graphene nanocomposite material, step include：
1), graphite oxide is disperseed in deionized water, supersound process obtains graphene oxide solution ie in solution A.
2), by nickel salt obtained nickel salt aqueous solution soluble in water, then nickel salt aqueous solution is added in solution A, at ultrasound
Reason obtains solution B；
3) then that vitamin C or trisodium citrate is molten, by vitamin C or trisodium citrate obtained solution soluble in water
Liquid is added in solution B, and supersound process obtains solution C；It is preferred that vitamin c solution is added in solution B, supersound process obtains solution
C；
4), by urea or hexa obtained solution soluble in water, then by urea liquid or hexa
Solution is added in solution C, and supersound process obtains solution D；It is preferred that urea liquid is added in solution C by after, supersound process obtains
Solution D；
5), solution D is transferred in reaction kettle and is reacted 8~24 hours at 90~240 DEG C, preferably at 120~180 DEG C
Reaction 10~18 hours；
6), product washs, and nickel hydroxide/graphene nanocomposite material is obtained after dry.
Step 1) the graphite oxide is prepared by improved Hummers methods, and specific preparation method is：5.0g stones are weighed respectively
Ink and 3.75g NaNO3It is put into the beaker of 1L, mechanical strong stirring, is slowly added to the concentrated sulfuric acid of 150mL, stir 0.5 hour,
It is slow added into the KMnO of 20g4, add within 0.5 hour, after continuing stirring 20 hours, reactant viscosity increases, and stops stirring, obtains
To the purplish red color substance of starchiness.After placing 5 days, it is respectively added slowly to 500mL deionized waters and 30mL H2O2, solution colour at this time
Become obvious glassy yellow, after solution fully reacts, centrifugation, washing obtain graphene oxide.
A concentration of 0.05~1.0mg/mL of graphene oxide solution, preferably 0.1~0.8mg/mL in the step 1)；It is super
The sound time is 30~60 minutes, and the temperature of water is 5~50 DEG C in Ultrasound Instrument；
Nickel salt is selected from one or more of nickel chloride, nickel nitrate, nickel acetate, nickel salt concentration 0.04 in the step 2)
~0.6mol/L, preferably 0.1~0.4mol/L；Ultrasonic time is 15~60 minutes, and the temperature of water is 5~50 DEG C in Ultrasound Instrument；
A concentration of 0.14~0.85mol/L of vitamin C or citric acid three sodium solution in the step 3), preferably 0.2~
0.6mol/L；Ultrasonic time is 15~60 minutes；The temperature of water is 5~50 DEG C in Ultrasound Instrument；Dimension can also be used in step 3)
The mixed solution of raw element C and trisodium citrate, in mixed solution the total concentration of vitamin C and trisodium citrate for 0.14~
0.85mol/L, preferably 0.2~0.6mol/L；
Urea or hexa solution a concentration of 0.16mol/L~1.8mol/L in the step 4), preferably 0.4~
1.6mol/L；Ultrasonic time is 15~60 minutes；The temperature of water is 5~50 DEG C in Ultrasound Instrument；Can make in step 4) urea and
The mixed solution of hexa, the total concentration of urea and hexa is 0.16~1.8mol/L in mixed solution,
It is preferred that 0.4~1.6mol/L；
Washing is respectively with deionized water, ethyl alcohol sedimentation washing, 60 DEG C of dryings, sedimentation washing in the step 6)；
The 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 of nickel hydroxide/graphene nanocomposite material；
A kind of ultracapacitor, including electrode of super capacitor made of nickel hydroxide/graphene nanocomposite material
It is made.
The present invention mechanism be：The functional groups of nickel ion and surface of graphene oxide, urea divide under the high temperature conditions
A large amount of OH are generated after solution, hydrolysis-, OH-It is combined to form nickel hydroxide with nickel ion again, i.e., nickel hydroxide is in situ on the surface of graphene
Growth, formed using graphene as base material and on the surface of graphene growth in situ at nickel hydroxide nano piece nano combined material
Material.
The present invention is by compound mode in the graphene surface load transitions with high-specific surface area and satisfactory electrical conductivity
Metal hydroxides prepares graphene-based composite material.Synergistic effect between composite material each component can make each component mutual
It maximizes favourable factors and minimizes unfavourable ones：In combination with the high than electricity of the high circulation service life of electric double layer capacitance, high power density, high stability and fake capacitance
Hold characteristic, to improve the comprehensive performance of ultracapacitor.In graphene-based composite material, in transition metal hydroxide electricity
High conductivity graphene is introduced in extremely may increase its electric conductivity；And if graphene surface is modified by transition metal hydroxide
(load), then graphene can be prevented from being piled into sheet again, this can be such that its polymerization minimizes, and electrochemical contact area is maximum
Change.For this point, the advantages of graphene/transition metal hydroxide nanocomposite of synthesis can use for reference other side,
To which two electrode material performances improve jointly.The utilization rate for improving fake capacitance electrode material in this way, improves compound
The performance of material.
Compared with the prior art, the present invention has the following advantages：
(1) nickel hydroxide/graphene nanocomposite material obtained by is in integrally three-dimensional porous shape, nickel hydroxide nano piece
Direct growth in situ on the surface of graphene；
(2) growth in situ can prevent the accumulation again of graphene to nickel hydroxide nano piece on the surface of graphene, improve stone
The specific surface area utilization rate of black alkene；
(3) growth in situ, graphene can improve the conductivity of nickel hydroxide to nickel hydroxide nano piece on the surface of graphene,
So as to improve its chemical property；
(4) preparation method of nickel hydroxide/graphene nanocomposite material of the invention it is simple, it is mild, environmentally protective and
The advantages that at low cost.
Description of the drawings
Fig. 1 is the SEM figures of nickel hydroxide/graphene nanocomposite material prepared by embodiment 1.
Fig. 2 is the XRD diagram of nickel hydroxide/graphene nanocomposite material prepared by embodiment 2.
Fig. 3 is the SEM figures of nickel hydroxide/graphene nanocomposite material prepared by embodiment 2.
Fig. 4 is the SEM figures of nickel hydroxide/graphene nanocomposite material prepared by embodiment 3.
Fig. 5 is the SEM figures of nickel hydroxide/graphene nanocomposite material prepared by embodiment 4.
Fig. 6 is the SEM figures of nickel hydroxide/graphene nanocomposite material prepared by embodiment 5.
Fig. 7 is the TEM figures of nickel hydroxide/graphene nanocomposite material prepared by embodiment 5.
Fig. 8 is cycle of the nickel hydroxide/graphene nanocomposite material of the preparation of embodiment 5 under 0.5A/g current densities
Stability test figure.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail.Embodiments of the present invention are not limited thereto.
Embodiment 1
The preparation of graphite oxide：5.0g graphite and 3.75g NaNO are weighed respectively3It is put into the beaker of 1L, machinery strength is stirred
It mixes, is slowly added to the concentrated sulfuric acid of 150mL, stir 0.5 hour, be slow added into the KMnO of 20g4, add within 0.5 hour, continue to stir
After mixing 20 hours, reactant viscosity increases, and stops stirring, obtains the purplish red color substance of starchiness.After placing 5 days, slowly add respectively
Enter 500mL deionized waters and 30mLH2O2, at this time solution colour become obvious glassy yellow, after solution fully reacts, from
The heart, washing, obtain graphite oxide.
5.0mg graphite oxides are taken, are dispersed in 100mL deionized waters, ultrasound obtains solution A for 1 hour, and control water temperature is 5
~40 DEG C, the present embodiment water temperature is 25 DEG C.It weighs 0.6g Nickel dichloride hexahydrates to be dissolved in 20mL deionized waters, add after stirring evenly
Enter in solution A, ultrasound obtains solution B in 30 minutes.It takes 0.5g vitamin Cs to be dissolved in 15mL deionized waters, is stirring evenly and then adding into
In solution B, ultrasound obtains solution C in 30 minutes.It takes 0.3g urea to be dissolved in 15mL deionized waters, is stirring evenly and then adding into solution C
In, ultrasonic 20 minutes solution obtains solution D.Solution D is poured into the ptfe autoclave of 200mL, 140 DEG C of reactions 24 are small
When.
Product is used respectively deionized water and ethyl alcohol sedimentation wash 4 times, and 12 hours dry at 30 DEG C, obtains hydroxide
Nickel/graphene nanocomposite material.
Embodiment 2
The preparation method is the same as that of Example 1 for graphite oxide.10.0mg graphite oxides are taken, are dispersed in 100mL deionized waters, are surpassed
Sound obtains solution A for 1 hour, and for control water temperature at 5~40 DEG C, the present embodiment water temperature is 30 DEG C.It is molten to weigh 1.2g Nickel dichloride hexahydrates
It in 20mL deionized waters, is stirring evenly and then adding into solution A, ultrasound obtains solution B in 30 minutes.1.0g vitamin Cs are taken to be dissolved in
It in 15mL deionized waters, is stirring evenly and then adding into solution B, ultrasound obtains solution C in 30 minutes.It takes 0.6g urea to be dissolved in 15mL to go
It in ionized water, is stirring evenly and then adding into solution C, ultrasonic 20 minutes solution obtains solution D.Solution D is poured into poly- the four of 200mL
In vinyl fluoride reaction kettle, 120 DEG C are reacted 24 hours.
Product is used respectively deionized water and ethyl alcohol sedimentation wash 3 times, and 10 hours dry at 60 DEG C, obtains hydroxide
Nickel/graphene nanocomposite material.
Embodiment 3
The preparation method is the same as that of Example 1 for graphite oxide.20.0mg graphite oxides are taken, are dispersed in 100mL deionized waters, are surpassed
Sound obtains solution A for 1 hour, and for control water temperature at 5~40 DEG C, the present embodiment water temperature is 30 DEG C.It is molten to weigh 1.6g Nickel dichloride hexahydrates
It in 20mL deionized waters, is stirring evenly and then adding into solution A, ultrasound obtains solution B in 30 minutes.1.0g vitamin Cs are taken to be dissolved in
It in 15mL deionized waters, is stirring evenly and then adding into solution B, ultrasound obtains solution C in 30 minutes.It takes 0.8g urea to be dissolved in 15mL to go
It in ionized water, is stirring evenly and then adding into solution C, ultrasonic 20 minutes solution obtains solution D.Solution D is poured into poly- the four of 200mL
In vinyl fluoride reaction kettle, 140 DEG C are reacted 12 hours.
Product is used to deionized water and ethyl alcohol sedimentation washing 3 times respectively, and dry 6 hours at 80 DEG C, obtain nickel hydroxide/
Graphene nanocomposite material.
Embodiment 4
The preparation method is the same as that of Example 1 for graphite oxide.30.0mg graphite oxides are taken, are dispersed in 100mL deionized waters, are surpassed
Sound obtains solution A for 1 hour, and for control water temperature at 5~40 DEG C, the present embodiment water temperature is 30 DEG C.It weighs 2.0g nickel nitrates and is dissolved in 20mL
It in deionized water, is stirring evenly and then adding into solution A, ultrasound obtains solution B in 30 minutes.It takes 2.0g vitamin Cs to be dissolved in 15mL to go
It in ionized water, is stirring evenly and then adding into solution B, ultrasound obtains solution C in 30 minutes.1.0g urea is taken to be dissolved in 15mL deionized waters
In, it is stirring evenly and then adding into solution C, ultrasonic 20 minutes solution obtains solution D.Solution D is poured into the polytetrafluoroethylene (PTFE) of 200mL
In reaction kettle, 160 DEG C are reacted 18 hours.
Product is used respectively deionized water and ethyl alcohol sedimentation wash 5 times, and 4 hours dry at 100 DEG C, obtains hydroxide
Nickel/graphene nanocomposite material.
Embodiment 5
The preparation method is the same as that of Example 1 for graphite oxide.50.0mg graphite oxides are taken, are dispersed in 100mL deionized waters, are surpassed
Sound obtains solution A for 1 hour, and for control water temperature at 5~40 DEG C, the present embodiment water temperature is 30 DEG C.It is molten to weigh 3.0g Nickel dichloride hexahydrates
It in 20mL deionized waters, is stirring evenly and then adding into solution A, ultrasound obtains solution B in 30 minutes.3.0g vitamin Cs are taken to be dissolved in
It in 15mL deionized waters, is stirring evenly and then adding into solution B, ultrasound obtains solution C in 30 minutes.Take 2.0g hexas molten
It in 15mL deionized waters, is stirring evenly and then adding into solution C, ultrasonic 20 minutes solution obtains solution D.Solution D is poured into
In the ptfe autoclave of 200mL, 200 DEG C are reacted 10 hours.
Product is used respectively deionized water and ethyl alcohol sedimentation wash 3 times, and 3 hours dry at 120 DEG C, obtains hydroxide
Nickel/graphene nanocomposite material.
Using 5 gained final product nickel hydroxide of example/graphene nanocomposite material as the electrode material of ultracapacitor
Material, uses the mass ratio of composite material, acetylene black and PTFE for 85:10:5, it is modulated into homogeneous solution by solvent of ethyl alcohol, it will be molten
Liquid is coated in 1cm2Nickel foam on, in vacuum drying chamber 60 DEG C dry 12 hours.To being coated with composite material after the completion of drying
Nickel foam carries out compressing tablet process.Electrochemical property test is carried out to material using three-electrode system, in ultracapacitor in 0.5A/
Cyclical stability test chart under g current densities is as shown in Fig. 8.By attached drawing 8 as it can be seen that the cyclical stability of ultracapacitor is good
It is good, still retain 90% or more of initial capacitance after recycling 1000 times.
Claims (16)
1. a kind of nickel hydroxide/graphene nanocomposite material, by base material graphene and in the life in situ of base material graphene surface
The nickel hydroxide nano piece composition grown up to, composite material are in integrally three-dimensional porous structure；
The preparation method step of the composite material includes：
1), graphite oxide is disperseed in deionized water, supersound process obtains graphene oxide solution ie in solution A；
2), by nickel salt obtained nickel salt aqueous solution soluble in water, then nickel salt aqueous solution is added in solution A, is ultrasonically treated
To solution B；
3), by vitamin C or trisodium citrate obtained solution soluble in water, then vitamin C or citric acid three sodium solution are added
Enter in solution B, supersound process obtains solution C；
4), by urea or hexa obtained solution soluble in water, then by urea liquid or hexa solution
It is added in solution C, supersound process obtains solution D；
5), solution D is transferred in reaction kettle and is reacted 8~24 hours at 90~240 DEG C；
6), product washs, and nickel hydroxide/graphene nanocomposite material is obtained after dry.
2. composite material as described in claim 1, which is characterized in that the preparation method step of the composite material includes：
1), graphite oxide is disperseed in deionized water, supersound process obtains graphene oxide solution ie in solution A；
2), by nickel salt obtained nickel salt aqueous solution soluble in water, then nickel salt aqueous solution is added in solution A, is ultrasonically treated
To solution B；
3), by vitamin C obtained solution soluble in water, then vitamin c solution is added in solution B, supersound process obtains molten
Liquid C；
4), by urea obtained solution soluble in water, then urea liquid is added in solution C, supersound process obtains solution D；
5), solution D is transferred in reaction kettle and is reacted 10~18 hours at 120~180 DEG C；
6), product washs, and nickel hydroxide/graphene nanocomposite material is obtained after dry.
3. a kind of preparation method of nickel hydroxide/graphene nanocomposite material, step include：
1), graphite oxide is disperseed in deionized water, supersound process obtains graphene oxide solution ie in solution A；
2), by nickel salt obtained nickel salt aqueous solution soluble in water, then nickel salt aqueous solution is added in solution A, is ultrasonically treated
To solution B；
3), by vitamin C or trisodium citrate obtained solution soluble in water, then vitamin C or citric acid three sodium solution are added
Enter in solution B, supersound process obtains solution C；
4), by urea or hexa obtained solution soluble in water, then by urea liquid or hexa solution
It is added in solution C, supersound process obtains solution D；
5), solution D is transferred in reaction kettle and is reacted 8~24 hours at 90~240 DEG C；
6), product washs, and nickel hydroxide/graphene nanocomposite material is obtained after dry.
4. preparation method as claimed in claim 3, it is characterised in that：The preparation method step includes：
1), graphite oxide is disperseed in deionized water, supersound process obtains graphene oxide solution ie in solution A；
2), by nickel salt obtained nickel salt aqueous solution soluble in water, then nickel salt aqueous solution is added in solution A, is ultrasonically treated
To solution B；
3), by vitamin C obtained solution soluble in water, then vitamin c solution is added in solution B, supersound process obtains molten
Liquid C；
4), by urea obtained solution soluble in water, then urea liquid is added in solution C, supersound process obtains solution D；
5), solution D is transferred in reaction kettle and is reacted 10~18 hours at 120~180 DEG C；
6), product washs, and nickel hydroxide/graphene nanocomposite material is obtained after dry.
5. preparation method as claimed in claim 3, it is characterised in that：Graphene oxide solution is a concentration of in the step 1)
0.05~1.0mg/mL；Ultrasonic time is 30~60 minutes, and the temperature of water is 5~50 DEG C in Ultrasound Instrument.
6. preparation method as claimed in claim 5, it is characterised in that：Graphene oxide solution is a concentration of in the step 1)
0.1~0.8mg/mL.
7. preparation method as claimed in claim 3, it is characterised in that：In the step 2) nickel salt be selected from nickel chloride, nickel nitrate,
One or more of nickel acetate, a concentration of 0.04~0.6mol/L of nickel salt aqueous solution；Ultrasonic time is 15~60 minutes, ultrasound
The temperature of water is 5~50 DEG C in instrument.
8. preparation method as claimed in claim 7, it is characterised in that：A concentration of 0.1~the 0.4mol/L of nickel salt aqueous solution.
9. preparation method as claimed in claim 3, it is characterised in that：Vitamin C or trisodium citrate are molten in the step 3)
A concentration of 0.14~0.85mol/L of liquid；Ultrasonic time is 15~60 minutes；The temperature of water is 5~50 DEG C in Ultrasound Instrument.
10. preparation method as claimed in claim 9, it is characterised in that：Vitamin C or trisodium citrate are molten in the step 3)
A concentration of 0.2~0.6mol/L of liquid.
11. preparation method as claimed in claim 3, it is characterised in that：Urea or hexa are molten in the step 4)
A concentration of 0.16~1.8mol/L of liquid；Ultrasonic time is 15~60 minutes；The temperature of water is 5~50 DEG C in Ultrasound Instrument.
12. preparation method as claimed in claim 11, it is characterised in that：Urea or hexa are molten in the step 4)
A concentration of 0.4~1.6mol/L of liquid.
13. preparation method as claimed in claim 3, it is characterised in that：In the step 6) washing for use respectively deionized water,
Ethyl alcohol sedimentation washing, 30~120 DEG C of dryings 3~12 hours.
14. preparation method as claimed in claim 3, it is characterised in that：The graphene oxide solution, nickel salt aqueous solution, dimension
Give birth to element C or citric acid three sodium solution, the volume ratio of urea or hexa solution is 20：4：3：3.
15. a kind of electrode of super capacitor is made of nickel hydroxide/graphene nanocomposite material described in claim 1.
16. a kind of ultracapacitor, by being made including the electrode of super capacitor described in claim 15.
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| CN106340391A (en) * | 2016-11-07 | 2017-01-18 | 珠海格力电器股份有限公司 | Graphene/nickel hydroxide composite material and preparation method thereof, and electrode material |
| CN106735299B (en) * | 2016-12-20 | 2019-03-05 | 哈尔滨工业大学（威海） | A kind of preparation method of graphene microchip load nanometer nickle composite powder |
| CN107502886A (en) * | 2017-07-13 | 2017-12-22 | 天津大学 | The preparation method of fabricated in situ sheet metal hydroxide/oxide composite |
| CN107644743A (en) * | 2017-08-25 | 2018-01-30 | 天津大学 | A kind of preparation method of the three-dimensional porous nitrogen-doped graphene of self-supporting-nickel hydroxide electrochemical capacitance electrode material |
| CN109675604A (en) * | 2019-01-07 | 2019-04-26 | 江苏大学 | Nickel hydroxide/thin layer carbonitride compounded visible light photocatalyst and preparation method thereof |
| CN109903997A (en) * | 2019-02-21 | 2019-06-18 | 江苏先创新能源有限公司 | A kind of porous laminated combination electrode material and preparation method and application |
| 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 |
| CN111348689B (en) * | 2020-02-12 | 2022-06-07 | 杭州电子科技大学 | A kind of Ni (OH)2Graphene composite material and preparation method 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 |
| 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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| CN105140044B (en) * | 2015-07-30 | 2017-12-19 | 中国科学院山西煤炭化学研究所 | A kind of method for preparing graphene-based nickel oxide nano composite |
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