CN106683909A - In-situ preparation method for cubic copper oxide/graphene aerogel composite material - Google Patents
In-situ preparation method for cubic copper oxide/graphene aerogel composite material Download PDFInfo
- Publication number
- CN106683909A CN106683909A CN201710049118.7A CN201710049118A CN106683909A CN 106683909 A CN106683909 A CN 106683909A CN 201710049118 A CN201710049118 A CN 201710049118A CN 106683909 A CN106683909 A CN 106683909A
- Authority
- CN
- China
- Prior art keywords
- graphene
- copper
- oxide
- aerogel composite
- graphene aerogel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 85
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 39
- 239000004964 aerogel Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 238000004108 freeze drying Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000010791 quenching Methods 0.000 claims abstract description 11
- 230000000171 quenching effect Effects 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 238000000859 sublimation Methods 0.000 claims description 6
- 230000008022 sublimation Effects 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 abstract 1
- 238000004506 ultrasonic cleaning Methods 0.000 abstract 1
- 230000008901 benefit Effects 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000013066 combination product Substances 0.000 description 5
- 229940127555 combination product Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002114 nanocomposite Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 206010027476 Metastases Diseases 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- -1 lithium (sodium) ion Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000009401 metastasis Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/23—
-
- B01J35/39—
-
- 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
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses an in-situ preparation method for a cubic copper oxide/graphene aerogel composite material. The method comprises the following steps of: S1) putting a copper net into 1-3M hydrochloric acid, absolute ethyl alcohol and deionized water in turn, performing ultrasonic cleaning and then drying; S2) dispersing graphene oxide into the deionized water and ultrasonically treating for 1-3 hours, thereby acquiring a graphene oxide dispersion liquid in the concentration of 1-5mg mL-1; S3) pouring the graphene oxide dispersion liquid acquired in the step S2) into an autoclave liner, putting the copper net acquired in the step S1) into the autoclave liner and performing hydrothermal reaction, wherein the temperature of the hydrothermal reaction is at 120-200 DEG C and the reaction time is 6-15h; and S4) taking out the product acquired from the step S3), quenching and performing freeze drying, thereby acquiring the copper oxide/graphene aerogel composite material, wherein the freeze drying time is 12-48h, the freeze drying temperature is at -30 to -50 DEG C and the vacuum degree is at 10-30Pa.
Description
Technical field
The present invention relates to transition metal oxide-carbon nanomaterial field, more particularly to a kind of cubic oxide copper/graphite
The in-situ preparation method of alkene aerogel composite.
Background technology
Used as a kind of metal oxide semiconductor, its energy gap is 1.7 electron-volts to copper oxide, can absorb visible ray,
The application of the aspects such as photoelectric device, photoelectrocatalysiss, energy storage and conversion, various kinds of sensors is can be applicable to, with environmental friendliness,
Stable chemical performance, high efficiency, low cost and other advantages.Used as a kind of two-dimension nano materials, it has good dispersion to Graphene, electricity
Transport factor is high, nontoxic, the advantages of specific surface area is big.Graphene is by going back the oxidation stone that reason Hummers method is prepared
What black alkene was obtained, the advantage of the method is that course of reaction is relatively mild, is had more compared with for the methods such as chemical vapour deposition technique
High yield, preparation cost is relatively low.The surface of graphene oxide and marginal distribution have substantial amounts of hydroxyl and carboxyl, therefore
It shows good hydrophilic, can be dispersed in water, and above-mentioned hydroxyl and carboxyl can be tied with metal cation
Close, therefore dispersed metal cation can be gone using graphene oxide, metal cation is uniformly distributed in graphenic surface, then
Metal oxide/graphene composite material is obtained by the process of specific method.
The composite that the metal-oxide that Graphene is loaded with it is formed can show under certain condition cooperative effect.
When energy storage device is applied to, the negative material of such as lithium ion battery or sodium-ion battery, copper oxide/Graphene composite wood
Material can utilize its interfacial effect, increased the storage density and cyclical stability of lithium (sodium) ion；Also, due to Graphene
With higher carrier mobility, this is conducive to the migration of electric charge, increased the charge-discharge velocity of battery.In light-catalyzed reaction
In, the catalysis activity of single metal-oxide is relatively low, is primarily due to these metal-oxides and sends out during the course of the reaction
A certain degree of reunion is given birth to, has caused active reaction sites to reduce, the efficiency of photo-generated carrier has declined, so as to cause photocatalysis anti-
Should middle catalytic rate reduction；Because Graphene has larger specific surface area, when metal-oxide is carried on as light absorbent
When the surface and edge of Graphene, the separation and migration of photo-generated carrier can be effectively lifted, reduce photo-generated carrier
Recombination rate again, therefore construct the composite construction of copper oxide/Graphene and be conducive to improving its light-catalysed reaction rate.
Mohit Saraf etc. pass through hydrothermal template in the 2826-2833 above-reporteds of ChemistrySelect 1 (2016)
Method has synthesized oxidation copper micron ball, then is dispersed in supersound process in graphite oxide aqueous solution and has obtained copper oxide and Graphene
Combination product, for the research of ultracapacitor.Yuhua Shen etc. are in Ceramics International 42 (2016)
Report on 1833-1839 with carbamide as foaming agent, copper nitrate and graphene oxide are disperseed in deionized water, by hydro-thermal
Method prepares the complex of copper oxide and Graphene, for the research of lithium ion battery.Youcheng Zhao etc. exist
It is that copper source and reducing agent pass through the legal system that flows back to report on the 6710-6719 of CrystEngComm 14 (2012) and adopt Cu-lyt.
The standby combination product for obtaining copper oxide and Graphene, have studied its electrocatalysis characteristic.
The research having had at present has many weakness in the preparation of this combination product, is first the numerous of synthetic method
Trivial complexity, the addition/removal of template and the stirring of ultra-long time etc. all cause reaction condition to become harsh, it is necessary to the chemistry of addition
Medicine had not only polluted environment but also had caused the cost of sinteticses to raise；Another aspect is then that the pattern of combination product is not good, is combined
The copper oxide of product is more with the presentation of irregular granular powder so that its electrochemical energy storage performance and photocatalytic activity are lifted not
Height, and the recycling of powder body catalyst is a difficult problem.Therefore, one environmentally friendly, with low cost, step is simple
Preparation method obtain that pattern is excellent and graphene composite material of performance boost be in the urgent need to.
The content of the invention
In order to solve defect present in prior art, the invention provides one kind does not need long agitation, does not need
The article that add/go removing template, must add is pollution-free and low cost, combination product morphology controllable, electrochemical energy storage performance and
Photocatalytic activity is higher, photocatalyst facilitate recycling cubic oxide copper/graphene aerogel composite original position
Preparation method.
Technical scheme：The in-situ preparation method of cubic oxide copper/graphene aerogel composite of the present invention, its
It is characterised by：Comprise the following steps：
S1：Copper mesh is sequentially placed in hydrochloric acid, dehydrated alcohol and deionized water and is cleaned by ultrasonic, be then dried place
Reason；
S2：Graphene oxide is disperseed in deionized water, ultrasound, obtain concentration for 1~5mg mL-1Graphene oxide
Dispersion liquid；
S3：Pour the graphene oxide dispersion that step S2 is obtained into autoclave inner bag, then be put into in autoclave inner bag
The copper mesh that step S1 is obtained, carries out hydro-thermal reaction, and hydrothermal temperature is 120~200 DEG C, and the response time is 6~15h；
S4：The product that step S3 is obtained takes out, and carries out quenching and lyophilization, obtains copper oxide/graphene aerogel
Composite；Sublimation drying is 12~48h, and lyophilization temperature is -30~-50 DEG C, and vacuum is 10~30Pa.
Further, the quenching in step S4 is the quenching in liquid nitrogen.
Further, the concentration of hydrochloric acid in step S1 is 1~3M.So can effectively remove the oxide layer on copper mesh surface
And impurity.
Further, the ultrasonic time in step S2 is 1~3 hour.Can so make graphene oxide dispersed.
Beneficial effect：Compared with prior art, the present invention has following beneficial effect：
1) preparation process is simple of the present invention, is easily controlled, with low cost pollution-free, is easy to high-volume commercial production；It is made
Standby graphene aerogel has specific surface area big, the advantages of stable chemical nature, good conductivity, adjustable aperture；Copper oxide/stone
Black alkene composite morphology controllable, good crystallinity, uniform particle diameter and microscopic appearance are cube, and cubic oxide copper nano particles are equal
It is grown in evenly on aeroge, takes full advantage of the unique three dimensional structure of graphene aerogel and high specific surface area.
2) substrate that the present invention is selected is the copper mesh with three-dimensional net structure, and copper simple substance has very strong reproducibility, and
The surface of graphene oxide and marginal distribution have substantial amounts of hydroxyl and carboxyl, and they can be combined with metal cation, make metal
Cation is uniformly distributed in graphenic surface.Therefore, one step hydro thermal method can be prepared simply and effectively with three-dimensional porous
The graphene aerogel of structure and high-specific surface area, there is provided more copper oxide nanometer particle growth sites, effectively suppresses oxygen
Change the reunion of copper.Graphene aerogel has excellent electric conductivity so that during photocatalytic degradation and electrochemical redox
Electronics can be transmitted with effective and rapid, can effectively lift the efficiency of electric charge transmission, given full play to the excellent light of copper oxide and urged
Change and electrochemical energy storage performance；The loose structure of graphene aerogel is conducive to the infiltration and migration of electrolyte ion, further
Improve the chemical property of composite.Additionally, copper mesh is free of contamination raw material.
3) present invention direct growth porous nanometer material in copper mesh substrate, on the one hand can increase active material with conduction
The effective contact area of substrate；On the other hand, the regular pore canal structure constructed can accelerate electronics and electrolyte ion in electrode
In transfer rate, being finally reached improves the purpose of material electrochemical performance.Additionally, the nano material of synthesis can be used directly
Do electrode, it is to avoid traditional powder active material prepares the cumbersome process of electrode and the addition of insulating polymer binding agent；
Photocatalytic applications aspect, this photocatalyst being grown directly upon in conductive substrates is more convenient compared to powder body catalyst to be reclaimed again
Utilize, with good environment-friendly advantage, and the separation and transmission of carrier can be effectively facilitated in photocatalytic process, can
Effectively improve photocatalytic activity.
4) step of growth in situ one that the present invention realizes gelation and copper oxide by simple hydro-thermal method is completed.Meanwhile,
Copper oxide is compound with Graphene so that both advantages are given full play to, compound with multilevel hierarchy so as to construct
Material, can be used as the ideal electrode material of the novel energy such as high-performance optical catalyst material and lithium ion battery, ultracapacitor
Material.
Description of the drawings
Fig. 1 be the embodiment of the present invention it is 2-in-1 into copper oxide/graphene nanocomposite material XRD spectrum；
Fig. 2 be the embodiment of the present invention it is 2-in-1 into copper oxide/graphene nanocomposite material Raman collection of illustrative plates；
Fig. 3 be the embodiment of the present invention it is 2-in-1 into copper oxide/graphene nanocomposite material scanning electron microscope low
Photo under enlargement ratio；
Fig. 4 be the embodiment of the present invention it is 2-in-1 into copper oxide/graphene nanocomposite material scanning electron microscope in height
Photo under enlargement ratio；
Fig. 5 be the embodiment of the present invention it is 2-in-1 into copper oxide/graphene nanocomposite material transmission electron microscope shine
Piece.
Specific embodiment
The present invention prepares cubic oxide copper/graphene aerogel composite by simple technological design.This is answered
Condensation material has obvious advantage：Copper mesh not only provided copper source but also had served as the flexible substrates of electrode material, used as playing through bridge
The effect of connection copper oxide/graphene sheet layer, the special construction of three-dimensional conductive network also provides good for electrochemical reaction
Electronics and ion diffusion admittance, shorten the diffusion length of ion, so as to reduce the internal resistance of active electrode, are conducive to electricity
Transmission, the transfer between electrolyte and electrode material such as son, ion；And the graphene sheet layer of two dimension is mainly as structure gel three
The module of building of dimension physical cross-linked network structure plays a part of skeletal support.Graphene aerogel can be cubic oxide copper
Growth provides the substrate of a high-specific surface area, it is suppressed that the reunion of copper oxide, and effectively exposes the work of cubic oxide copper
Property edge；The loose structure of graphene aerogel is also beneficial to the migration in electrochemical reaction process intermediate ion, shortens electrolysis
Route of metastasis of the matter to avtive spot.Therefore, both are effectively combined, are capable of achieving good synergism, to prepare
Go out highly active composite.
With reference to embodiment and accompanying drawing, technical scheme is further introduced.
Embodiment 1：
Present embodiment discloses a kind of in-situ preparation method of cubic oxide copper/graphene aerogel composite, including
Following steps：
S1：Copper mesh is sequentially placed in 1M hydrochloric acid, dehydrated alcohol and deionized water and is cleaned by ultrasonic, be then dried
Process；
S2：100mg graphene oxides are dispersed in 100ml deionized waters, ultrasound 1 hour, obtain concentration for 1mg mL-1
Graphene oxide dispersion；
S3：Pour the graphene oxide dispersion that step S2 is obtained into autoclave inner bag, then be put into in autoclave inner bag
The copper mesh that step S1 is obtained, carries out hydro-thermal reaction, and hydrothermal temperature is 160 DEG C, and the response time is 10h；
S4：The product that step S3 is obtained takes out, and carries out quenching and lyophilization, obtains copper oxide/graphene aerogel
Composite；Sublimation drying is 12h, and lyophilization temperature is -30 DEG C, and vacuum is 10Pa.
Embodiment 2：
Present embodiment discloses a kind of in-situ preparation method of cubic oxide copper/graphene aerogel composite, including
Following steps：
S1：Copper mesh is sequentially placed in 3M hydrochloric acid, dehydrated alcohol and deionized water and is cleaned by ultrasonic, be then dried
Process；
S2：200mg graphene oxides are dispersed in 100ml deionized waters, ultrasound 2 hours, obtain concentration for 2mg mL-1
Graphene oxide dispersion；
S3：Pour the graphene oxide dispersion that step S2 is obtained into autoclave inner bag, then be put into in autoclave inner bag
The copper mesh that step S1 is obtained, carries out hydro-thermal reaction, and hydrothermal temperature is 180 DEG C, and the response time is 12h；
S4：The product that step S3 is obtained takes out, and carries out quenching and lyophilization, obtains copper oxide/graphene aerogel
Composite；Sublimation drying is 15h, and lyophilization temperature is -50 DEG C, and vacuum is 10Pa.
The XRD spectrum of the copper oxide that the present embodiment is prepared/graphene aerogel composite is as shown in Figure 1, it is seen that
The degree of crystallinity of the composite for preparing is very high, without dephasign.As a result show：Copper oxide/graphene aerogel composite
There is a wider diffraction maximum in 2 θ=26.0 °, corresponding to (002) crystal face of redox graphene；Additionally, the three strongest ones of collection of illustrative plates
Peak (2 θ angles are 36.4 °, 42.3 °, 61.4 °) coincide with the three strongest peak of the standard card (JCPDS NO.67-850) of copper oxide,
Illustrate that copper oxide nanometer particle has successfully been carried on aerogel composite.
The Raman figure of the copper oxide that the present embodiment is prepared/graphene aerogel composite is as shown in Fig. 2 obtain
Composite is 1349 and 1595cm-1Place produces all larger Raman scattering peak of intensity and peak width, and sp is corresponded to respectively3Hydridization carbon
Interatomic A1gVibration (D peaks) and sp2E between hydbridized carbon atoms2gVibration (G peaks), in addition 295,342 and 626cm-1The three of place
Individual Raman peaks correspond to respectively the A of copper oxideg, Bg 1And Bg 1Vibration peak.Copper oxide coexists with graphite Raman characteristic peak, explanation
The two defines complex.
The SEM figures of the copper oxide that the present embodiment is prepared/graphene aerogel composite, as shown in figure 3, oxidation
Copper/graphene aerogel composite has multi-stage pore structure, and graphene sheet layer completely covers copper mesh, be built into three-dimensional network
Structure, cubic oxide copper nano particles are evenly distributed in graphene sheet layer, and particle diameter is about 500-700nm.As can be seen from Figure 4 oxygen
Change copper cubic granules can well be assembled on redox graphene piece and form composite.Prepared copper oxide/stone
Black alkene aerogel composite has unique loose structure, and copper oxide nanometer particle is equably grown on Graphene, effectively
Inhibit the reunion of copper oxide itself, the activity of the copper oxide nanometer particle with high electrochemical activity edge is obtained fully
Exposure.
Embodiment 3：
Present embodiment discloses a kind of in-situ preparation method of cubic oxide copper/graphene aerogel composite, including
Following steps：
S1：Copper mesh is sequentially placed in 3M hydrochloric acid, dehydrated alcohol and deionized water and is cleaned by ultrasonic, be then dried
Process；
S2：300mg graphene oxides are dispersed in 100ml deionized waters, ultrasound 3 hours, obtain concentration for 3mg mL-1
Graphene oxide dispersion；
S3：Pour the graphene oxide dispersion that step S2 is obtained into autoclave inner bag, then be put into in autoclave inner bag
The copper mesh that step S1 is obtained, carries out hydro-thermal reaction, and hydrothermal temperature is 200 DEG C, and the response time is 15h；
S4：The product that step S3 is obtained takes out, and carries out quenching and lyophilization, obtains copper oxide/graphene aerogel
Composite；Sublimation drying is 24h, and lyophilization temperature is -40 DEG C, and vacuum is 10Pa.
Embodiment 4：
Present embodiment discloses a kind of in-situ preparation method of cubic oxide copper/graphene aerogel composite, including
Following steps：
S1：Copper mesh is sequentially placed in 2M hydrochloric acid, dehydrated alcohol and deionized water and is cleaned by ultrasonic, be then dried
Process；
S2：500mg graphene oxides are dispersed in 100ml deionized waters, ultrasound 3 hours, obtain concentration for 5mg mL-1
Graphene oxide dispersion；
S3：Pour the graphene oxide dispersion that step S2 is obtained into autoclave inner bag, then be put into in autoclave inner bag
The copper mesh that step S1 is obtained, carries out hydro-thermal reaction, and hydrothermal temperature is 120 DEG C, and the response time is 6h；
S4：The product that step S3 is obtained takes out, and carries out quenching and lyophilization, obtains copper oxide/graphene aerogel
Composite；Sublimation drying is 48h, and lyophilization temperature is -50 DEG C, and vacuum is 30Pa.
Claims (4)
1. a kind of in-situ preparation method of cubic oxide copper/graphene aerogel composite, it is characterised in that：Including following step
Suddenly：
S1：Copper mesh is sequentially placed in hydrochloric acid, dehydrated alcohol and deionized water and is cleaned by ultrasonic, be then dried process；
S2：Graphene oxide is disperseed in deionized water, ultrasound, obtain concentration for 1~5mg mL-1Graphene oxide dispersion
Liquid；
S3：Pour the graphene oxide dispersion that step S2 is obtained into autoclave inner bag, then step is put into in autoclave inner bag
The copper mesh that S1 is obtained, carries out hydro-thermal reaction, and hydrothermal temperature is 120~200 DEG C, and the response time is 6~15h；
S4：The product that step S3 is obtained takes out, and carries out quenching and lyophilization, obtains copper oxide/graphene aerogel and is combined
Material；Sublimation drying is 12~48h, and lyophilization temperature is -30~-50 DEG C, and vacuum is 10~30Pa.
2. the in-situ preparation method of cubic oxide copper/graphene aerogel composite according to claim 1, its feature
It is：Quenching in step S4 is the quenching in liquid nitrogen.
3. the in-situ preparation method of cubic oxide copper/graphene aerogel composite according to claim 1, its feature
It is：Concentration of hydrochloric acid in step S1 is 1~3M.
4. the in-situ preparation method of cubic oxide copper/graphene aerogel composite according to claim 1, its feature
It is：Ultrasonic time in step S2 is 1~3 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710049118.7A CN106683909B (en) | 2017-01-23 | 2017-01-23 | A kind of in-situ preparation method of cubic oxide copper/graphene aerogel composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710049118.7A CN106683909B (en) | 2017-01-23 | 2017-01-23 | A kind of in-situ preparation method of cubic oxide copper/graphene aerogel composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106683909A true CN106683909A (en) | 2017-05-17 |
| CN106683909B CN106683909B (en) | 2018-05-18 |
Family
ID=58859916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710049118.7A Expired - Fee Related CN106683909B (en) | 2017-01-23 | 2017-01-23 | A kind of in-situ preparation method of cubic oxide copper/graphene aerogel composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106683909B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109399781A (en) * | 2019-01-02 | 2019-03-01 | 广东石油化工学院 | The catalysis of support type graphene produces potentiometric titrations oxidation processes waste water from dyestuff method |
| CN109637844A (en) * | 2018-11-27 | 2019-04-16 | 中国电子科技集团公司第十八研究所 | Preparation method of positive electrode composite material for lithium ion capacitor |
| CN110860287A (en) * | 2019-11-07 | 2020-03-06 | 湖北工业大学 | Preparation method of graphene/copper nanocrystalline composite catalytic material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102765715A (en) * | 2012-07-12 | 2012-11-07 | 上海大学 | Graphene-loaded lamellar cupric oxide composite material and hydro-thermal synthesis method thereof |
| CN103295799A (en) * | 2013-06-17 | 2013-09-11 | 华东理工大学 | Cuprous oxide and grapheme composited nanometer material production method |
| CN103474257A (en) * | 2013-09-16 | 2013-12-25 | 哈尔滨工程大学 | Preparation method for graphene oxide load cupric oxide lithium ion capacitor electrode materials |
| CN103578796A (en) * | 2013-11-15 | 2014-02-12 | 复旦大学 | Preparation method of super-capacitor electrode without adhesives |
| CN103956473A (en) * | 2014-05-20 | 2014-07-30 | 浙江师范大学 | CuO-Cu2O/graphene nano compound material and preparation method thereof |
| CN104801244A (en) * | 2015-04-09 | 2015-07-29 | 浙江理工大学 | Method for preparing three-dimensional graphene-copper nanowire composite aerogel |
| CN105772741A (en) * | 2016-04-26 | 2016-07-20 | 中国科学院深圳先进技术研究院 | Three-dimensional structure aerogel with copper nanowires coated with graphene and preparation method of three-dimensional structure aerogel and application of three-dimensional structure aerogel |
-
2017
- 2017-01-23 CN CN201710049118.7A patent/CN106683909B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102765715A (en) * | 2012-07-12 | 2012-11-07 | 上海大学 | Graphene-loaded lamellar cupric oxide composite material and hydro-thermal synthesis method thereof |
| CN103295799A (en) * | 2013-06-17 | 2013-09-11 | 华东理工大学 | Cuprous oxide and grapheme composited nanometer material production method |
| CN103474257A (en) * | 2013-09-16 | 2013-12-25 | 哈尔滨工程大学 | Preparation method for graphene oxide load cupric oxide lithium ion capacitor electrode materials |
| CN103578796A (en) * | 2013-11-15 | 2014-02-12 | 复旦大学 | Preparation method of super-capacitor electrode without adhesives |
| CN103956473A (en) * | 2014-05-20 | 2014-07-30 | 浙江师范大学 | CuO-Cu2O/graphene nano compound material and preparation method thereof |
| CN104801244A (en) * | 2015-04-09 | 2015-07-29 | 浙江理工大学 | Method for preparing three-dimensional graphene-copper nanowire composite aerogel |
| CN105772741A (en) * | 2016-04-26 | 2016-07-20 | 中国科学院深圳先进技术研究院 | Three-dimensional structure aerogel with copper nanowires coated with graphene and preparation method of three-dimensional structure aerogel and application of three-dimensional structure aerogel |
Non-Patent Citations (1)
| Title |
|---|
| BING ZHAO 等: "Hierarchical self-assembly of microscale leaf-like CuO on graphene sheets for high-performance electrochemical capacitors", 《J. MATER.CHEM.A》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109637844A (en) * | 2018-11-27 | 2019-04-16 | 中国电子科技集团公司第十八研究所 | Preparation method of positive electrode composite material for lithium ion capacitor |
| CN109399781A (en) * | 2019-01-02 | 2019-03-01 | 广东石油化工学院 | The catalysis of support type graphene produces potentiometric titrations oxidation processes waste water from dyestuff method |
| CN109399781B (en) * | 2019-01-02 | 2021-09-07 | 广东石油化工学院 | Method for treating dye wastewater by free radical oxidation for producing sulfate radicals under catalysis of supported graphene |
| CN110860287A (en) * | 2019-11-07 | 2020-03-06 | 湖北工业大学 | Preparation method of graphene/copper nanocrystalline composite catalytic material |
| CN110860287B (en) * | 2019-11-07 | 2022-08-19 | 湖北工业大学 | Preparation method of graphene/copper nanocrystalline composite catalytic material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106683909B (en) | 2018-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106914265B (en) | method for preparing nitrogen-doped porous nano carbon material by using biomass as carbon source through gel method | |
| CN102730680B (en) | High-density high-rigidity graphene porous carbon material as well as preparation method and applications thereof | |
| CN105597791B (en) | A kind of selenizing molybdenum/porous carbon nanofiber composite material and preparation method and application | |
| CN108390014B (en) | Preparation method of foam nickel loaded cobalt monoxide nano material with different morphologies | |
| CN108341404B (en) | Three-dimensional porous boron-carbon-nitrogen material and preparation method and application thereof | |
| CN107946084A (en) | A kind of metal oxide/three-dimensional porous graphene composite material and its preparation method and application | |
| CN106783230B (en) | A kind of titanium carbide growth in situ CNTs three-dimensional composite material and preparation method thereof | |
| CN109778225A (en) | A kind of N, S codope graphene/selenizing molybdenum/CoFe-LDH aeroge and its preparation | |
| Pang et al. | Wood-derived bimetallic and heteroatomic hierarchically porous carbon aerogel for rechargeable flow Zn–air batteries | |
| CN106025244A (en) | Nickel selenide/graphene/carbon nanotube composite material and preparation method thereof | |
| CN102718250A (en) | Method for preparing carbon-material-carrying tin dioxide nanosheet composite material | |
| CN106784706B (en) | A kind of carbon microspheres are as transition zone titanium carbide growth in situ CNTs three-dimensional composite material and preparation method thereof | |
| CN104401977A (en) | Preparation method of graphene aerogel and graphene-carbon nanotube aerogel | |
| CN110289424A (en) | A kind of preparation method of MOF derived carbon and cellular porous carbon composite | |
| CN106219510A (en) | The method that a kind of highly basic activation pomelo peel prepares three-dimensional carbon nano material | |
| CN105712303B (en) | A kind of selenizing molybdenum nanometer sheet/fiber base carbon aerogel composite material and preparation method thereof | |
| CN104269514A (en) | A preparing method of a transition metal compound-graphene composite material with a three-dimensional porous structure | |
| CN103227327A (en) | Pyrolysis preparation method of two-dimensional nano-sheet-layer lithium ion battery negative electrode material | |
| CN111313029A (en) | Closely-combined high-performance silicon/graphitized carbon composite material with hollow structure and preparation method and application thereof | |
| CN106683909B (en) | A kind of in-situ preparation method of cubic oxide copper/graphene aerogel composite material | |
| CN108772079A (en) | A kind of preparation method of nanometer of black phosphorus/graphene composite material | |
| Liu et al. | Interfacing CdS particles on Ni foam as a three-dimensional monolithic photocatalyst for efficient visible-light-driven H2 evolution | |
| Maouche et al. | Thermal treated three-dimensional N-doped graphene as efficient metal free-catalyst for oxygen reduction reaction | |
| CN109167077B (en) | Phosphorus-doped porous carbon-oxygen reduction catalyst and preparation method and application thereof | |
| Wang et al. | Rice-husk-derived mesoporous 0D/2D C3N4 isotype heterojunction with improved quantum effect for photodegradation of tetracycline antibiotics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180518 |