CN106683909B - A kind of in-situ preparation method of cubic oxide copper/graphene aerogel composite material - Google Patents
A kind of in-situ preparation method of cubic oxide copper/graphene aerogel composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 87
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 46
- 239000010949 copper Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 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
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000005751 Copper oxide Substances 0.000 claims abstract description 38
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 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
- 238000010791 quenching Methods 0.000 claims abstract description 11
- 230000000171 quenching effect Effects 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 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
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 238000000859 sublimation Methods 0.000 claims abstract description 7
- 230000008022 sublimation Effects 0.000 claims abstract description 7
- 238000002604 ultrasonography Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 description 10
- 230000008901 benefit Effects 0.000 description 8
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- 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
- 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
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- 239000003054 catalyst Substances 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
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002114 nanocomposite Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 150000001768 cations Chemical class 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
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
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- 239000004575 stone Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 206010027476 Metastases Diseases 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002091 cationic group Chemical group 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
- 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
- 239000013078 crystal Substances 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 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
- 239000004088 foaming agent Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 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
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 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
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
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- 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
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of in-situ preparation methods of cubic oxide copper/graphene aerogel composite material, comprise the following steps：S1：Copper mesh is sequentially placed into 1~3M hydrochloric acid, absolute ethyl alcohol and deionized water and is cleaned by ultrasonic, processing is then dried；S2：Graphene oxide is disperseed in deionized water, when ultrasound 1~3 is small, obtains concentration as 1~5mg mL‑1Graphene oxide dispersion；S3：The obtained graphene oxide dispersions of step S2 are poured into autoclave liner, then the copper mesh that step S1 is obtained is put into autoclave liner, carry out hydro-thermal reaction, hydrothermal temperature is 120~200 DEG C, and the reaction time is 6~15h；S4：The product that step S3 is obtained takes out, and carries out quenching and is freeze-dried, obtains copper oxide/graphene aerogel composite material；Sublimation drying is 12~48h, and freeze-drying temperature is 30~50 DEG C, and vacuum degree is 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
Copper oxide is 1.7 electron-volts as a kind of metal oxide semiconductor, energy gap, can absorb visible ray,
Can be applied to photoelectric device, photoelectrocatalysis, energy storage and the application of conversion, various kinds of sensors etc., have it is environmental-friendly,
Stable chemical performance, high efficiency, it is at low cost the advantages that.Graphene is as a kind of two-dimension nano materials, with good dispersion, electricity
The advantages that transport factor is high, nontoxic, large specific surface area.Graphene is the oxidation stone being prepared by going back reason Hummers methods
What black alkene obtained, the advantages of the method, is that reaction process is relatively mild, has more compared with for the methods of chemical vapour deposition technique
High yield, manufacturing cost are relatively low.The surface of graphene oxide and edge distribution have substantial amounts of hydroxyl and carboxyl, therefore
It shows good hydrophily, can uniformly disperse in water, and above-mentioned hydroxyl and carboxyl can be with metal cation knots
It closes, therefore can go dispersed metal cationic using graphene oxide, metal cation is made to be uniformly distributed in graphene surface, then
It handles to obtain metal oxide/graphene composite material by specific method.
The composite material that the metal oxide that graphene is loaded with it is formed can show synergistic effect under certain condition.
When applied to energy storage device, for example, the negative material of lithium ion battery or sodium-ion battery, copper oxide/graphene composite wood
Material can utilize its interfacial effect, add 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 charge, adds the charge-discharge velocity of battery.In light-catalyzed reaction
In, the catalytic activity of single metal oxide is relatively low, is primarily due to these metal oxides and sends out during the reaction
A degree of reunion has been given birth to, active reaction sites is caused to reduce, the efficiency of photo-generated carrier declines, anti-so as to cause photocatalysis
It should middle catalytic rate reduction；Since 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 promoted, reduces photo-generated carrier
Recombination rate again, therefore the composite construction for constructing copper oxide/graphene is conducive to improve its light-catalysed reaction rate.
Mohit Saraf etc. pass through hydrothermal template in ChemistrySelect 1 (2016) 2826-2833 above-reporteds
Method has synthesized oxidation copper micron ball, then is dispersed in be ultrasonically treated 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)
It is reported on 1833-1839 using urea as foaming agent, copper nitrate and graphene oxide is disperseed in deionized water, pass through hydro-thermal
The compound of copper oxide and graphene is prepared in method, for the research of lithium ion battery.Youcheng Zhao etc. exist
Being reported on CrystEngComm 14 (2012) 6710-6719 uses stannous chloride to pass through the legal system that flows back for copper source and reducing agent
It is standby to obtain the combination product of 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 the numerous of synthetic method first
Trivial complexity, 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
Drug not only polluted environment but also the cost of sintetics caused to raise；Another aspect is then that the pattern of combination product is bad, compound
The copper oxide of product is mostly presented with irregular granular powder so that its electrochemical energy storage performance and photocatalytic activity are promoted not
Height, and the recycling of powder catalyst is a problem.Therefore, one environmentally friendly, of low cost, step is simple
Preparation method obtain that pattern is excellent and the graphene composite material of performance boost be there is an urgent need to.
The content of the invention
In order to solve defect in the prior art, long agitation is not required the present invention provides one kind, is not required
The article that add/go removing template, must add is pollution-free and at low cost, combination product morphology controllable, electrochemical energy storage performance and
Photocatalytic activity is higher, photochemical catalyst facilitate recycling cubic oxide copper/graphene aerogel composite material original position
Preparation method.
Technical solution：The in-situ preparation method of cubic oxide copper/graphene aerogel composite material of the present invention,
It is characterized in that：Comprise the following steps：
S1：Copper mesh is sequentially placed into hydrochloric acid, absolute ethyl alcohol and deionized water and is cleaned by ultrasonic, place is then dried
Reason；
S2：Graphene oxide is disperseed in deionized water, ultrasound, obtain concentration as 1~5mg mL-1Graphene oxide
Dispersion liquid；
S3：The obtained graphene oxide dispersions of step S2 are poured into autoclave liner, then are put into autoclave liner
The copper mesh that step S1 is obtained carries out hydro-thermal reaction, and hydrothermal temperature is 120~200 DEG C, and the reaction time is 6~15h；
S4：The product that step S3 is obtained takes out, and carries out quenching and is freeze-dried, obtains copper oxide/graphene aerogel
Composite material；Sublimation drying is 12~48h, and freeze-drying temperature is -30~-50 DEG C, and vacuum degree is 10~30Pa.
Further, the quenching in the step S4 is the quenching in liquid nitrogen.
Further, the concentration of hydrochloric acid in the step S1 is 1~3M.It so can effectively remove the oxide layer on copper mesh surface
And impurity.
Further, when the ultrasonic time in the step S2 is 1~3 small.Can so graphene oxide be uniformly dispersed.
Advantageous effect：Compared with prior art, the present invention has following advantageous effect：
1) preparation process of the present invention is simple, is easy to control, of low cost pollution-free, convenient for high-volume industrial production；It is made
Standby graphene aerogel has many advantages, such as large specific surface area, and chemical property stabilization, good conductivity, aperture is adjustable；Copper oxide/stone
Black alkene composite material 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 three-dimensional structure of graphene aerogel uniqueness and high specific surface area.
2) substrate that the present invention selects is the copper mesh for having three-dimensional net structure, and copper simple substance has very strong reproducibility, and
The surface of graphene oxide and edge distribution have substantial amounts of hydroxyl and carboxyl, they can be combined with metal cation, make metal
Cation is uniformly distributed in graphene surface.Therefore, one step hydro thermal method can be simply and effectively prepared with three-dimensional porous
The graphene aerogel of structure and high-specific surface area provides more copper oxide nanometer particle growth sites, effectively inhibits oxygen
Change the reunion of copper.Graphene aerogel has excellent electric conductivity so that during photocatalytic degradation and electrochemical redox
Electronics can transmit effective and rapidly, can effectively promote the efficiency of charge transmission, give full play to the excellent light of copper oxide and urged
Change and electrochemical energy storage performance；The porous structure of graphene aerogel is conducive to the infiltration and migration of electrolyte ion, further
Improve the chemical property of composite material.In addition, copper mesh is free of contamination raw material.
3) on the one hand present invention direct growth porous nanometer material in copper mesh substrate can increase active material and conduction
Effective contact area of substrate；On the other hand, the regular pore canal structure constructed can accelerate electronics and electrolyte ion in electrode
In transmission rate, be finally reached improve material electrochemical performance purpose.In addition, the nano material of synthesis can be used directly
Electrode is done, avoids the addition of the cumbersome process and insulating polymer binding agent of traditional powder active material preparation electrode；
In terms of photocatalytic applications, this photochemical catalyst being grown directly upon in conductive substrates is more convenient recycling again compared to powder catalyst
It utilizes, there is good environment-friendly advantage, and the separation and transmission of carrier can be effectively facilitated in photocatalytic process, it can
Effectively improve photocatalytic activity.
4) present invention realizes gelation and one step of the growth in situ completion of copper oxide by simple hydro-thermal method.Meanwhile
Copper oxide and graphene it is compound so that the advantage of the two is given full play to, and has the compound of multilevel hierarchy so as to construct
Material can be used as the ideal electrode material of the novel energies such as high-performance optical catalyst material and lithium ion battery, ultracapacitor
Material.
Description of the drawings
Fig. 1 is the XRD spectrum for copper oxide/graphene nanocomposite material that the embodiment of the present invention 2 synthesizes；
Fig. 2 is the Raman collection of illustrative plates for copper oxide/graphene nanocomposite material that the embodiment of the present invention 2 synthesizes；
Fig. 3 is the scanning electron microscope for copper oxide/graphene nanocomposite material that the embodiment of the present invention 2 synthesizes low
Photo under enlargement ratio；
Fig. 4 is the scanning electron microscope for copper oxide/graphene nanocomposite material that the embodiment of the present invention 2 synthesizes in height
Photo under enlargement ratio；
Fig. 5 is that the transmission electron microscope for copper oxide/graphene nanocomposite material that the embodiment of the present invention 2 synthesizes shines
Piece.
Specific embodiment
Cubic oxide copper/graphene aerogel composite material is prepared by simple technological design in the present invention.This is multiple
Condensation material has apparent advantage：Copper mesh not only provided copper source but also had served as the flexible substrates of electrode material, was played as through bridge
The effect of copper oxide/graphene sheet layer is connected, 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 the role 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 expose the work of cubic oxide copper
Property edge；The porous structure of graphene aerogel is also beneficial to the migration in electrochemical reaction process intermediate ion, shortens electrolysis
Matter is to the route of metastasis of active site.Therefore, the two is carried out it is effectively compound, it can be achieved that good synergistic effect, to prepare
Go out the composite material of high activity.
With reference to embodiment and attached 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 material, including
Following steps：
S1：Copper mesh is sequentially placed into 1M hydrochloric acid, absolute ethyl alcohol and deionized water and is cleaned by ultrasonic, is then dried
Processing；
S2：100mg graphene oxides are dispersed in 100ml deionized waters, when ultrasound 1 is small, obtain concentration as 1mg mL-1
Graphene oxide dispersion；
S3：The obtained graphene oxide dispersions of step S2 are poured into autoclave liner, then are put into autoclave liner
The copper mesh that step S1 is obtained carries out hydro-thermal reaction, and hydrothermal temperature is 160 DEG C, reaction time 10h；
S4：The product that step S3 is obtained takes out, and carries out quenching and is freeze-dried, obtains copper oxide/graphene aerogel
Composite material；Sublimation drying is 12h, and freeze-drying temperature is -30 DEG C, vacuum degree 10Pa.
Embodiment 2：
Present embodiment discloses a kind of in-situ preparation method of cubic oxide copper/graphene aerogel composite material, including
Following steps：
S1：Copper mesh is sequentially placed into 3M hydrochloric acid, absolute ethyl alcohol and deionized water and is cleaned by ultrasonic, is then dried
Processing；
S2：200mg graphene oxides are dispersed in 100ml deionized waters, when ultrasound 2 is small, obtain concentration as 2mg mL-1
Graphene oxide dispersion；
S3：The obtained graphene oxide dispersions of step S2 are poured into autoclave liner, then are put into autoclave liner
The copper mesh that step S1 is obtained carries out hydro-thermal reaction, and hydrothermal temperature is 180 DEG C, reaction time 12h；
S4：The product that step S3 is obtained takes out, and carries out quenching and is freeze-dried, obtains copper oxide/graphene aerogel
Composite material；Sublimation drying is 15h, and freeze-drying temperature is -50 DEG C, vacuum degree 10Pa.
The XRD spectrum of the copper oxide that the present embodiment is prepared/graphene aerogel composite material is as shown in Figure 1, it is seen that
The crystallinity for the composite material being prepared is very high, without dephasign.The result shows that：Copper oxide/graphene aerogel composite material
In 2 θ=26.0 ° there are one wider diffraction maximum, corresponding to (002) crystal face of redox graphene；In addition, the three strongest ones of collection of illustrative plates
Peak (2 θ angles are 36.4 °, 42.3 °, 61.4 °) and the three strongest peak of the standard card (JCPDS NO.67-850) of copper oxide are coincide,
Illustrate that copper oxide nanometer particle is successfully carried on aerogel composite.
The Raman figure of the copper oxide that the present embodiment is prepared/graphene aerogel composite material is as shown in Fig. 2, obtain
Composite material is in 1349 and 1595cm-1Place generates intensity and all larger Raman scattering peak of peak width, corresponds to sp respectively3Hydridization carbon
Interatomic A1gVibrate (D peaks) and sp2E between hydbridized carbon atoms2gIt vibrates at (G peaks), in addition 295,342 and 626cm-1The three of place
A Raman peaks correspond to the A of copper oxide respectivelyg, Bg 1And Bg 1Vibration peak.Copper oxide coexists with graphite Raman characteristic peak, explanation
The two forms compound.
The SEM figures of the copper oxide that the present embodiment is prepared/graphene aerogel composite material, as shown in figure 3, oxidation
Copper/graphene aerogel composite material has multi-stage pore structure, and graphene sheet layer completely covers copper mesh, is built into three-dimensional network
Structure, cubic oxide copper nano particles are evenly distributed in graphene sheet layer, and grain size is about 500-700nm.As can be seen from Figure 4 oxygen
Redox graphene on piece formation composite material can be assembled in well by changing copper cubic granules.Prepared copper oxide/stone
Black alkene aerogel composite has unique porous structure, and copper oxide nanometer particle is equably grown on graphene, effectively
Ground inhibits the reunion of copper oxide itself, makes to have the copper oxide nanometer particle activity edge of high electrochemical activity to obtain fully
Exposure.
Embodiment 3：
Present embodiment discloses a kind of in-situ preparation method of cubic oxide copper/graphene aerogel composite material, including
Following steps：
S1：Copper mesh is sequentially placed into 3M hydrochloric acid, absolute ethyl alcohol and deionized water and is cleaned by ultrasonic, is then dried
Processing；
S2：300mg graphene oxides are dispersed in 100ml deionized waters, when ultrasound 3 is small, obtain concentration as 3mg mL-1
Graphene oxide dispersion；
S3：The obtained graphene oxide dispersions of step S2 are poured into autoclave liner, then are put into autoclave liner
The copper mesh that step S1 is obtained carries out hydro-thermal reaction, and hydrothermal temperature is 200 DEG C, reaction time 15h；
S4：The product that step S3 is obtained takes out, and carries out quenching and is freeze-dried, obtains copper oxide/graphene aerogel
Composite material；Sublimation drying is for 24 hours, freeze-drying temperature is -40 DEG C, vacuum degree 10Pa.
Embodiment 4：
Present embodiment discloses a kind of in-situ preparation method of cubic oxide copper/graphene aerogel composite material, including
Following steps：
S1：Copper mesh is sequentially placed into 2M hydrochloric acid, absolute ethyl alcohol and deionized water and is cleaned by ultrasonic, is then dried
Processing；
S2：500mg graphene oxides are dispersed in 100ml deionized waters, when ultrasound 3 is small, obtain concentration as 5mg mL-1
Graphene oxide dispersion；
S3：The obtained graphene oxide dispersions of step S2 are poured into autoclave liner, then are put into autoclave liner
The copper mesh that step S1 is obtained carries out hydro-thermal reaction, and hydrothermal temperature is 120 DEG C, reaction time 6h；
S4：The product that step S3 is obtained takes out, and carries out quenching and is freeze-dried, obtains copper oxide/graphene aerogel
Composite material；Sublimation drying is 48h, and freeze-drying temperature is -50 DEG C, vacuum degree 30Pa.
Claims (4)
1. a kind of in-situ preparation method of cubic oxide copper/graphene aerogel composite material, it is characterised in that：Including following step
Suddenly：
S1：Copper mesh is sequentially placed into hydrochloric acid, absolute ethyl alcohol and deionized water and is cleaned by ultrasonic, processing is then dried；
S2：Graphene oxide is disperseed in deionized water, ultrasound, obtain concentration as 1~5mg mL-1Graphene oxide disperse
Liquid；
S3：The obtained graphene oxide dispersions of step S2 are poured into autoclave liner, then step is put into autoclave liner
The copper mesh that S1 is obtained carries out hydro-thermal reaction, and hydrothermal temperature is 120~200 DEG C, and the reaction time is 6~15h；
S4：The product that step S3 is obtained takes out, and carries out quenching and is freeze-dried, it is compound to obtain copper oxide/graphene aerogel
Material；Sublimation drying is 12~48h, and freeze-drying temperature is -30~-50 DEG C, and vacuum degree is 10~30Pa.
2. the in-situ preparation method of cubic oxide copper/graphene aerogel composite material according to claim 1, feature
It is：Quenching in the step S4 is the quenching in liquid nitrogen.
3. the in-situ preparation method of cubic oxide copper/graphene aerogel composite material according to claim 1, feature
It is：Concentration of hydrochloric acid in the step S1 is 1~3M.
4. the in-situ preparation method of cubic oxide copper/graphene aerogel composite material according to claim 1, feature
It is：When ultrasonic time in the step S2 is 1~3 small.
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