CN106158416B - A kind of graphene/zinc oxide composite material of core-shell structure is the preparation method of the supercapacitor of cathode - Google Patents
A kind of graphene/zinc oxide composite material of core-shell structure is the preparation method of the supercapacitor of cathode Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 71
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000011258 core-shell material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000000243 solution Substances 0.000 claims abstract description 51
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007773 negative electrode material Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims abstract description 5
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 5
- 229960001545 hydrotalcite Drugs 0.000 claims description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 5
- 238000000527 sonication Methods 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000005253 cladding Methods 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000003990 capacitor Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OTFFCAGPSWJBDK-UHFFFAOYSA-N 1h-indazol-7-amine Chemical compound NC1=CC=CC2=C1NN=C2 OTFFCAGPSWJBDK-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004758 underpotential deposition Methods 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 the preparation methods for the supercapacitor that a kind of graphene/zinc oxide composite material of core-shell structure is cathode, comprising the following steps: (1) by graphene dispersion in n,N-Dimethylformamide, obtains graphene dispersing solution；(2) acetylacetone,2,4-pentanedione zinc powder is prepared；(3) acetylacetone,2,4-pentanedione zinc powder is added in graphene dispersing solution, stirring makes graphene surface coat zinc acetylacetonate；(4) the hydro-thermal reaction 1-48h at 50-250 DEG C obtains graphene/zinc oxide composite material of core-shell structure；(5) using graphene/zinc oxide composite material of core-shell structure as negative electrode material, negative electrode is prepared；(6) negative electrode is impregnated and carries out electrode activation processing in the electrolytic solution；(7) negative electrode is assembled into supercapacitor together with positive electrode.Supercapacitor specific capacity with higher prepared by the present invention, good cyclical stability.
Description
Technical field
The invention belongs to technology field of energy storage device, it is related to a kind of graphene/zinc oxide composite material of core-shell structure and is negative
The preparation method of the supercapacitor of pole.
Background technique
A kind of novel energy storage component between General Physics capacitor and secondary cell of supercapacitor, because of its conduct
The next-generation energy storage device of lithium ion battery can be substituted and attracted attention.The energy that this novel energy storage component is stored, phase
Than more than General Physics capacitor is order of magnitude greater；Meanwhile and maintain physical capacitor release energy it is fireballing excellent
Point can make up conventional batteries (such as lead-acid battery, nickel-metal hydride battery, lithium electricity battery) release slow disadvantage of electric energy.
According to the difference of energy storage mechanism, capacitor is divided into three classes according to Ultrahigh, electric double layer type capacitor, counterfeit electricity
Hold capacitor and has the hybrid capacitors of both the above capacitor specific characteristics concurrently.The Ultrahigh of electric double layer type capacitor and quiet
Electric type capacitor is identical, and the mechanism of accumulation is aligning in electrode/solution by electronics and ion or dipole
Interface forms electric double layer at interface, charge is stored between electrode and electrolyte interface, resulting capacitor is known as electric double layer
Capacitor.The mechanism that fake capacitance is formed is in electrode surface or body phase, and electroactive material carries out underpotential deposition, and height occurs can
Inverse chemisorption and redox reaction.In identical electrode area, double layer capacitor and fake capacitance capacitor
It compares, the capacitance of the latter is about the former 10 times；But fake capacitance capacitor be faced with poor circulation, working range it is narrow,
It charges the defects of slow.Therefore, using combination process, two kinds of materials have complementary advantages, and prepare hybrid super capacitor, at
For the hot spot studied at present.
Zinc oxide is high with energy density, power density is big, working range is wide, memory-less effect, charge-discharge velocity are fast, valence
The features such as lattice are cheap, environmentally friendly and be widely studied.But due to zinc load during the charging process uneven electro-deposition and
The special growth characteristics of zinc crystal, causing the deformation of zinc load even to fall off causes reduction and the zinc dendrite arm of zinc electrode capacity
Until puncturing diaphragm, serious restriction uses the capacity and cycle life of the supercapacitor of zinc load for growth.
It is in order to further increase the chemical property of material, zinc oxide and graphene progress is compound, it helps to improve multiple
The capacitance and cycle performance of condensation material.Graphene thickness is small, and it is a kind of good that intensity is big, high conductivity, high-specific surface area
Electrode material auxiliary agent.Such as in patent of invention, Qu Lai et al. (application number of invention patent: 201510495438.6) is disclosed
A kind of graphene metal composite electrode material for super capacitor and preparation method thereof.This method is successfully prepared for a kind of electrode
Material by flake graphite alkene and flake nano metal and/or flake nano metal alloy, conducting polymer it is compound obtain it is compound
Product, conducting polymer are embedded in adjacent metal plate layer and graphene film interlayer.Metal oxide can be successfully solved in this way
The poor defect of poorly conductive, stability；Meanwhile and can prevent graphene from reuniting and accumulating, surface can be utilized by improving graphene
Product.But since which employs the methods that micromechanics under vacuum condition is removed, preparation process is complicated, preparation environmental requirement is high, can
Control property is poor, and early investment is huge, and large-scale production difficulty is big.
Therefore a kind of mild condition is developed, is suitble to graphene/zinc oxide composite of large-scale industrial production, and will
It is applied in supercapacitor as negative electrode material and is of great significance.
Summary of the invention
It is an object of the invention to: in view of the problems of the existing technology, provide a kind of graphene/zinc oxide core-shell structure
Composite material is the preparation method of the supercapacitor of cathode, and the supercapacitor of preparation specific capacity with higher is good
Cyclical stability.
To achieve the goals above, the technical solution adopted by the present invention are as follows:
A kind of graphene/zinc oxide composite material of core-shell structure is the preparation method of the supercapacitor of cathode, including with
Lower step:
(1) by graphene dispersion in n,N-Dimethylformamide, graphene dispersing solution is obtained；
(2) Zn (NO is prepared respectively3)2Solution and acetylacetone,2,4-pentanedione solution, then by Zn (NO3)2Solution and acetylacetone,2,4-pentanedione solution are mixed
It closes, after stirring, it is 1~7 that ammonium hydroxide, which is added dropwise, and adjusts solution ph, continues to be stirred to react, then product is centrifuged or is filtered, is washed
It washs, it is dry, obtain acetylacetone,2,4-pentanedione zinc powder；
(3) the acetylacetone,2,4-pentanedione zinc powder that step (2) obtains is added in the graphene dispersing solution that step (1) obtains, stirring,
Graphene surface is set to coat zinc acetylacetonate；
(4) solution system that step (3) obtains is transferred in reaction kettle, the hydro-thermal reaction 1-48h at 50-250 DEG C, so
Product is centrifuged or is filtered afterwards, is washed, it is dry, obtain graphene/zinc oxide composite material of core-shell structure；
(5) graphene obtained using step (4)/zinc oxide composite material of core-shell structure is negative electrode material, by negative electrode material,
Conductive agent and binder are coated in collection liquid surface after mixing, carry out tabletting after dry, obtain negative electrode；
(6) negative electrode for obtaining step (5) impregnates carries out electrode activation processing in the electrolytic solution；
(7) by step (6), treated, and negative electrode assembles supercapacitor together with positive electrode.
As a preferred solution of the present invention, in the step (1), by graphene ultrasonic disperse in n,N-Dimethylformamide
In, sonication treatment time 1-10h, ultrasonic power 50-500W.
As a preferred solution of the present invention, in the step (2), Zn (NO3)2Ratio with acetylacetone,2,4-pentanedione is 100g:1L.
As a preferred solution of the present invention, in the step (3), the mass ratio of acetylacetone,2,4-pentanedione zinc powder and graphene is 1:
1。
As a preferred solution of the present invention, in the step (5), conductive agent is acetylene black, and binder is polytetrafluoroethylene (PTFE),
The mass ratio of negative electrode material, conductive agent and binder is 70-85:10-25:5.
As a preferred solution of the present invention, in the step (6), electrolyte is the KOH electrolytic of concentration 6mol/L
Liquid, activation processing time are 12h.
As a preferred solution of the present invention, in the step (7), positive electricity is extremely using nickel aluminum hydrotalcite as positive electrode system
Standby positive electrode.
The beneficial effects of the present invention are:
1. the present invention prepares super capacitor as negative electrode material using the graphene/zinc oxide composite material of core-shell structure prepared
Device, in the negative electrode material, nano granular of zinc oxide is placed between the interlayer of graphene film, using graphene by nano zine oxide
Grain is coated and fixed, to fundamentally inhibit the deformation of zinc load and the growth of zinc dendrite arm, improves the capacitor of supercapacitor
Amount and cycle life.
2. nano granular of zinc oxide is placed between the interlayer of graphene film, can make mutually to be separated by between graphene sheet layer
From, so that the characteristic of graphene large specific surface area is retained to reduce the agglomeration between graphene sheet layer significantly, and
And the synergistic effect of both graphene and zinc oxide can be obtained, greatly increase specific capacity.
3. because graphene has excellent electric conductivity quick " electron transport channel " can be formed, to greatly strengthen
The electric conductivity of electrode active material improves its chemical property.
Detailed description of the invention
Fig. 1 is graphene/zinc oxide composite material of core-shell structure low magnification scanning electron prepared by embodiment 1
Microscope photo；
Fig. 2 is graphene/zinc oxide composite material of core-shell structure high-amplification-factor scanning electron prepared by embodiment 1
Microscope photo；
Fig. 3 is cyclic voltammetry curve of the electrode in the case where 5mV/s sweeps speed prepared by embodiment 1；
Fig. 4 is the charging and discharging curve under electrode 1A/g current density prepared by embodiment 2；
Fig. 5 is the cycle life curve under electrode 1A/g current density prepared by embodiment 2.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with attached drawing to of the invention excellent
Embodiment is selected to be described in detail.
Embodiment 1
(1) take 50g graphene ultrasonic disperse in 50g n,N-Dimethylformamide, sonication treatment time 3h, ultrasound
Power is 200W, obtains graphene dispersing solution；
(2) 500g Zn (NO is taken3)2·6H2O solid is dissolved in 5L water, persistently stirs 30min, obtains Zn (NO3)2Solution；
It takes 5L acetylacetone,2,4-pentanedione, 5L water to be put into container, 500mL ammonium hydroxide is added, persistently stir 30min until acetylacetone,2,4-pentanedione dissolution, obtains
Acetylacetone,2,4-pentanedione solution；By Zn (NO3)2Solution and the mixing of acetylacetone,2,4-pentanedione solution, after stirring, it is 3 that ammonium hydroxide, which is added dropwise, and adjusts solution ph,
Continue to be stirred to react, then filter product, replaces washed product with water and ethyl alcohol, dry 12h at 80 DEG C obtains acetylacetone,2,4-pentanedione
Zinc powder；
(3) the acetylacetone,2,4-pentanedione zinc powder 50g that step (2) obtains is added in the graphene dispersing solution that step (1) obtains, is stirred
It mixes, graphene surface is made to coat zinc acetylacetonate；
(4) solution system that step (3) obtains is transferred in reaction kettle, hydro-thermal reaction for 24 hours, then will at 100 DEG C
Product filtering replaces washed product with water and ethyl alcohol, and dry 12h at 80 DEG C obtains graphene/zinc oxide core-shell structure composite wood
Material；
(5) for the graphene obtained using step (4)/zinc oxide composite material of core-shell structure as negative electrode material, acetylene black is to lead
Electric agent, polytetrafluoroethylene (PTFE) are binder, and negative electrode material, conductive agent and binder are dispersed in nothing according to mass ratio 80:15:5
In water-ethanol, ultrasonic 30min is allowed in the foamed nickel current collector for being coated onto 1cm × 1cm size after mixing, and 80 DEG C true
The dry 12h of sky obtains negative electrode by electrode tabletting 30 seconds under 10MPa pressure；
(6) negative electrode that step (5) obtains is immersed in the potassium hydroxide electrolyte of concentration 6mol/L, carries out electrode active
Change processing 12h；
(7) by step (6) treated negative electrode together with the positive electrode prepared using nickel aluminum hydrotalcite as positive electrode
Assemble supercapacitor.
Fig. 1 is graphene/zinc oxide composite material of core-shell structure low magnification scanning electron prepared by embodiment 1
Microscope photo, Fig. 2 are the scanning of graphene/zinc oxide composite material of core-shell structure high-amplification-factor prepared by embodiment 1
Electron micrograph, the material that as can be seen from the figure prepared by embodiment 1 have the following characteristics that nano granular of zinc oxide size
It is small, it is uniformly distributed between the interlayer of graphene film, nano granular of zinc oxide is coated and fixed graphene.
Selecting platinum electrode is to electrode, and saturated calomel electrode is reference electrode, made to embodiment 1 under three-electrode system
Standby negative electrode carries out electrochemical property test, and Fig. 3 is cyclic voltammetric of the electrode in the case where 5mV/s sweeps speed prepared by embodiment 1
Curve can be observed with apparent redox peaks in curve from figure.
Embodiment 2
(1) take 100g graphene ultrasonic disperse in 50g n,N-Dimethylformamide, sonication treatment time 2h, ultrasound
Power is 400W, obtains graphene dispersing solution；
(2) 1000g Zn (NO is taken3)2·6H2O solid is dissolved in 10L water, persistently stirs 30min, obtains Zn (NO3)2It is molten
Liquid；It takes 10L acetylacetone,2,4-pentanedione, 10L water to be put into container, 1000mL ammonium hydroxide is added, persistently stir 30min until acetylacetone,2,4-pentanedione is molten
Solution, obtains acetylacetone,2,4-pentanedione solution；By Zn (NO3)2Solution and the mixing of acetylacetone,2,4-pentanedione solution after stirring, are added dropwise ammonium hydroxide and adjust pH value of solution
Value is 6, continues to be stirred to react, then filters product, replaces washed product with water and ethyl alcohol, dry 12h at 80 DEG C obtains second
Acyl acetone zinc powder；
(3) the acetylacetone,2,4-pentanedione zinc powder 100g that step (2) obtains is added in the graphene dispersing solution that step (1) obtains,
Stirring makes graphene surface coat zinc acetylacetonate；
(4) solution system that step (3) obtains is transferred in reaction kettle, the hydro-thermal reaction 12h at 200 DEG C, then will
Product filtering replaces washed product with water and ethyl alcohol, and dry 12h at 80 DEG C obtains graphene/zinc oxide core-shell structure composite wood
Material；
(5) for the graphene obtained using step (4)/zinc oxide composite material of core-shell structure as negative electrode material, acetylene black is to lead
Electric agent, polytetrafluoroethylene (PTFE) are binder, and negative electrode material, conductive agent and binder are dispersed in nothing according to mass ratio 70:25:5
In water-ethanol, ultrasonic 30min is allowed in the foamed nickel current collector for being coated onto 1cm × 1cm size after mixing, and 80 DEG C true
The dry 12h of sky obtains negative electrode by electrode tabletting 30 seconds under 10MPa pressure；
(6) negative electrode that step (5) obtains is immersed in the potassium hydroxide electrolyte of concentration 6mol/L, carries out electrode active
Change processing 12h；
(7) by step (6) treated negative electrode together with the positive electrode prepared using nickel aluminum hydrotalcite as positive electrode
Assemble supercapacitor.
Fig. 4 is the charging and discharging curve under electrode 1A/g current density prepared by embodiment 2.Fig. 5 is prepared by embodiment 2
Electrode 1A/g current density under cycle life curve.As can be seen from the figure the negative electrode prepared has discharge time long,
The advantages of good cycling stability.
Embodiment 3
(1) take 20g graphene ultrasonic disperse in 50g n,N-Dimethylformamide, sonication treatment time 1h, ultrasound
Power is 100W, obtains graphene dispersing solution；
(2) 200g Zn (NO is taken3)2·6H2O solid is dissolved in 2L water, persistently stirs 30min, obtains Zn (NO3)2Solution；
It takes 2L acetylacetone,2,4-pentanedione, 2L water to be put into container, 200mL ammonium hydroxide is added, persistently stir 30min until acetylacetone,2,4-pentanedione dissolution, obtains
Acetylacetone,2,4-pentanedione solution；By Zn (NO3)2Solution and the mixing of acetylacetone,2,4-pentanedione solution, after stirring, it is 2 that ammonium hydroxide, which is added dropwise, and adjusts solution ph,
Continue to be stirred to react, then filter product, replaces washed product with water and ethyl alcohol, dry 12h at 80 DEG C obtains acetylacetone,2,4-pentanedione
Zinc powder；
(3) the acetylacetone,2,4-pentanedione zinc powder 20g that step (2) obtains is added in the graphene dispersing solution that step (1) obtains, is stirred
It mixes, graphene surface is made to coat zinc acetylacetonate；
(4) solution system that step (3) obtains is transferred in reaction kettle, the hydro-thermal reaction 48h at 70 DEG C, then will be produced
Object filtering replaces washed product with water and ethyl alcohol, and dry 12h at 80 DEG C obtains graphene/zinc oxide core-shell structure composite wood
Material；
(5) for the graphene obtained using step (4)/zinc oxide composite material of core-shell structure as negative electrode material, acetylene black is to lead
Electric agent, polytetrafluoroethylene (PTFE) are binder, and negative electrode material, conductive agent and binder are dispersed in nothing according to mass ratio 85:10:5
In water-ethanol, ultrasonic 30min is allowed in the foamed nickel current collector for being coated onto 1cm × 1cm size after mixing, and 80 DEG C true
The dry 12h of sky obtains negative electrode by electrode tabletting 30 seconds under 10MPa pressure；
(6) negative electrode that step (5) obtains is immersed in the potassium hydroxide electrolyte of concentration 6mol/L, carries out electrode active
Change processing 12h；
(7) by step (6) treated negative electrode together with the positive electrode prepared using nickel aluminum hydrotalcite as positive electrode
Assemble supercapacitor.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although passing through ginseng
According to the preferred embodiment of the present invention, invention has been described, it should be appreciated by those of ordinary skill in the art that can
To make various changes to it in the form and details, without departing from the present invention defined by the appended claims
Spirit and scope.
Claims (5)
1. a kind of graphene/zinc oxide composite material of core-shell structure is the preparation method of the supercapacitor of cathode, feature exists
In: the following steps are included:
(1) by graphene ultrasonic disperse in n,N-Dimethylformamide, sonication treatment time 1-10h, ultrasonic power 50-
500W obtains graphene dispersing solution；
(2) Zn (NO is prepared respectively3)2Solution and acetylacetone,2,4-pentanedione solution, then by Zn (NO3)2Solution and the mixing of acetylacetone,2,4-pentanedione solution, are stirred
After mixing, it is 1~7 that ammonium hydroxide, which is added dropwise, and adjusts solution ph, continues to be stirred to react, then product is centrifuged or is filtered, wash, do
It is dry, obtain acetylacetone,2,4-pentanedione zinc powder；
(3) the acetylacetone,2,4-pentanedione zinc powder that step (2) obtains is added in the graphene dispersing solution that step (1) obtains, stirring makes stone
The mass ratio of black alkene surface cladding zinc acetylacetonate, acetylacetone,2,4-pentanedione zinc powder and graphene is 1:1；
(4) solution system that step (3) obtains is transferred in reaction kettle, the hydro-thermal reaction 1-48h at 50-250 DEG C, then will
Product centrifugation or filtering, are washed, dry, obtain graphene/zinc oxide composite material of core-shell structure；
(5) graphene obtained using step (4)/zinc oxide composite material of core-shell structure is negative electrode material, by negative electrode material, conduction
Agent and binder are coated in collection liquid surface after mixing, carry out tabletting after dry, obtain negative electrode；
(6) negative electrode for obtaining step (5) impregnates carries out electrode activation processing in the electrolytic solution；
(7) by step (6), treated, and negative electrode assembles supercapacitor together with positive electrode.
2. the system that graphene according to claim 1/zinc oxide composite material of core-shell structure is the supercapacitor of cathode
Preparation Method, it is characterised in that: in the step (2), Zn (NO3)2Ratio with acetylacetone,2,4-pentanedione is 100g:1L.
3. the system that graphene according to claim 1/zinc oxide composite material of core-shell structure is the supercapacitor of cathode
Preparation Method, it is characterised in that: in the step (5), conductive agent is acetylene black, and binder is polytetrafluoroethylene (PTFE), and negative electrode material is led
The mass ratio of electric agent and binder is 70-85:10-25:5.
4. the system that graphene according to claim 1/zinc oxide composite material of core-shell structure is the supercapacitor of cathode
Preparation Method, it is characterised in that: in the step (6), electrolyte is the potassium hydroxide electrolyte of concentration 6mol/L, when activation processing
Between be 12h.
5. the system that graphene according to claim 1/zinc oxide composite material of core-shell structure is the supercapacitor of cathode
Preparation Method, it is characterised in that: in the step (7), positive electrode that positive electricity is extremely prepared using nickel aluminum hydrotalcite as positive electrode.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102906016A (en) * | 2010-04-22 | 2013-01-30 | 巴斯夫欧洲公司 | Method for producing two-dimensional sandwich nano-materials on the basis of graphene |
| CN103965876A (en) * | 2013-01-30 | 2014-08-06 | 海洋王照明科技股份有限公司 | Green-yellow light-emitting organic electroluminescent material, its preparation method and organic electroluminescent device |
| CN104701490A (en) * | 2015-04-02 | 2015-06-10 | 北京师范大学 | Preparing method and application of sandwich-structure graphene-based carbon cladding metal oxide |
| CN104769755A (en) * | 2012-09-29 | 2015-07-08 | 华东理工大学 | Methods and compositions for making metal oxide-graphene composites |
| CN104801292A (en) * | 2015-04-22 | 2015-07-29 | 哈尔滨工业大学 | Preparation method for zinc oxide hollow nanosphere/graphene composite material |
-
2016
- 2016-08-22 CN CN201610693194.7A patent/CN106158416B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102906016A (en) * | 2010-04-22 | 2013-01-30 | 巴斯夫欧洲公司 | Method for producing two-dimensional sandwich nano-materials on the basis of graphene |
| CN104769755A (en) * | 2012-09-29 | 2015-07-08 | 华东理工大学 | Methods and compositions for making metal oxide-graphene composites |
| CN103965876A (en) * | 2013-01-30 | 2014-08-06 | 海洋王照明科技股份有限公司 | Green-yellow light-emitting organic electroluminescent material, its preparation method and organic electroluminescent device |
| CN104701490A (en) * | 2015-04-02 | 2015-06-10 | 北京师范大学 | Preparing method and application of sandwich-structure graphene-based carbon cladding metal oxide |
| CN104801292A (en) * | 2015-04-22 | 2015-07-29 | 哈尔滨工业大学 | Preparation method for zinc oxide hollow nanosphere/graphene composite material |
Non-Patent Citations (9)
| Title |
|---|
| Solvothermal synthesis and characterization of sandwich-like graphene/ZnO nanocomposites;Jili Wu 等;《Applied Surface Science》;20091117;第256卷;第2826-2830页论文摘要、正文第2-3节以及图3 |
| ZnO@GQDs核壳结构量子点的制备及性能研究;施周 等;《发光学报》;20140228;第35卷(第2期);第137-141页 |
| 基于氧化锌和石墨烯超级电容器材料的研究进展;李艳芳 等;《广东化工》;20151215;第42卷(第23期);第116-118页 |
| 核壳结构氧化锌/石墨烯的光催化性能及机理研究;杨晓喻 等;《中国科学技术大学学报》;20140831;第44卷(第8期);第661-666页 |
| 氧化锌/石墨烯复合材料的水热制备及其光催化性能;马晶 等;《中国科技论文》;20150930;第10卷(第18期);第2130-2135页 |
| 水热法制备ZnO/石墨烯复合材料及其电化学性能研究;张利峰 等;《人工晶体学报》;20141231;第43卷(第12期);第3235-3240页 |
| 纳米氧化锌/石墨烯超级电容器材料研究进展;龚赢赢 等;《电子元件与材料》;20131130;第32卷(第11期);第6-10页 |
| 超级电容器用纳米氧化锌/石墨烯复合材料的制备与应用研究;龚赢赢;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20150415(第2015/04期);B020-74论文摘要及正文第5章 |
| 配合物前驱体水热制备纳米氧化锌及其光催化性能研究;陈海玉 等;《材料导报》;20131130;第27卷;第23-27页 |
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