CN107104006A - A kind of graphene@cupric silicates are classified heterogeneous nano composite material and its production and use - Google Patents
A kind of graphene@cupric silicates are classified heterogeneous nano composite material and its production and use Download PDFInfo
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- CN107104006A CN107104006A CN201710292290.5A CN201710292290A CN107104006A CN 107104006 A CN107104006 A CN 107104006A CN 201710292290 A CN201710292290 A CN 201710292290A CN 107104006 A CN107104006 A CN 107104006A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 91
- 239000000463 material Substances 0.000 title claims abstract description 56
- 150000004760 silicates Chemical class 0.000 title claims abstract description 46
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000005406 washing Methods 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- -1 graphite alkene Chemical class 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005119 centrifugation Methods 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- ZZBBCSFCMKWYQR-UHFFFAOYSA-N copper;dioxido(oxo)silane Chemical compound [Cu+2].[O-][Si]([O-])=O ZZBBCSFCMKWYQR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000007772 electrode material Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 2
- 229910003978 SiClx Inorganic materials 0.000 claims 2
- 238000005253 cladding Methods 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 claims 1
- 241001502050 Acis Species 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000012046 mixed solvent Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000011258 core-shell material Substances 0.000 description 10
- 239000003643 water by type Substances 0.000 description 10
- 239000002086 nanomaterial Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 241001466460 Alveolata Species 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- B01J35/39—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
Heterogeneous nano composite material and its preparation and application are classified the invention discloses a kind of graphene@cupric silicates.The material includes the shell that the nanometer cupric silicate for the kernel and needle-like being made up of flake graphite alkene is constituted；The nanometer cupric silicate of described needle-like is arranged on core surface in an array manner.Its preparation method comprises the following steps：(1) by graphene oxide ultrasonic disperse in the in the mixed solvent formed by surfactant, solvent, deionized water.(2) esters of silicon acis is added in above-mentioned solvent, a period of time is continuously stirred at room temperature.After centrifugation, washing, drying, the graphene oxide of coated with silica is obtained.(3) by the graphene oxide ultrasonic disperse of coated with silica in deionized water, add after a small amount of ammoniacal liquor and copper-containing compound, it is transferred in autoclave after being incubated 8~24h at 120 DEG C~160 DEG C and is cooled to room temperature in atmosphere, after centrifugation, washing, drying, obtains the material.Material prepared by the present invention can be as electrode material.
Description
Technical field
The invention belongs to technical field of nano material, more particularly to a kind of classification of graphene@cupric silicates are heterogeneous nano combined
The preparation of material.
Background technology
Classification nanostructure, be it is a kind of by simple nanostructured be main construction unit, such as nanoneedle, nanometer
Line, nanometer rods etc., are then assembled into the ordered structure of rule according to certain arrangement mode.Hierarchy has specific surface area
A series of excellent architectural features such as greatly, efficiency of light absorption is high, anti-agglomeration ability is strong.Therefore three-dimensional classification nanostructure not only has
There is the superior function that single module units is produced, and cooperative effect and coupling can be produced because of the arrangement assembling of construction unit
Effect is closed, new physicochemical properties are obtained.Thus material property is improved, application prospect is expanded.When the chemistry of its module units
When constituting different, heterogeneous classification nanostructure will be formed, heterogeneous interface can be formed.Therefore classification dissimilar materials is except with than table
Outside the advantages of area is big, efficiency of light absorption is high, anti-agglomeration ability is strong, the advantage of uniqueness is also obtained in terms of electric charge transmission.Super
The fields such as level capacitor, photocatalysis, solar cell and sewage disposal have huge application prospect.
Graphene be one kind by carbon atom with Sp2Planar film of the hybrid form close-packed arrays into alveolate texture.It is to only have
The two-dimensional sheet material of monoatomic layer thickness.Unique structure imparts a series of excellent electricity of graphene, calorifics, mechanical property
Energy and very high chemical stability, make it show to lure in fields such as nano-device, battery/ultracapacitor, composites
The application prospect of people.But Van der Waals force is larger between graphene, graphene film is easy to reunite.How graphene uniqueness knot is being kept
It is the problem of having to solve on graphene application road to be improved while structure and reduce its tendency reunited.
On the other hand, silicate is due to low cost, and physicochemical property uniqueness is also widely used in many application fields.And
When silicate material is Nano grade, the non-existent many speciality of conventional silicate can be showed, such as very big specific surface area,
High physical strength, opto-electronic conversion energy and electromagnetic wave absorption ability.It is widely used in sorbing material, catalysis material and electricity
Chemical sensor.But nano silicate material similarly faces surface energy height, the problem of easily reuniting.
Using graphite as stratum nucleare, cupric silicate prepares the heterogeneous nano composite material of graphene@cupric silicates classification for shell and will combined
Graphene and the respective advantage of cupric silicate.The core shell structure of formation not only prevents graphene and the respective reunion of nano silicate from inclining
To, and the contact area between graphene and cupric silicate can be promoted to maximize to strengthen the phase between graphene and silicic acid ketone
Mutual electric transmission effect.The classification dissimilar materials is expected to lead in ultracapacitor, photocatalysis, solar cell and sewage disposal etc.
Domain has potential huge applications prospect.
The content of the invention
It is an object of the invention to provide a kind of graphene@cupric silicates be classified heterogeneous nano composite material and preparation method thereof and
Using.
The present invention is realized using following technical scheme：
A kind of graphene@cupric silicates are classified heterogeneous nano composite material, and the graphene@cupric silicates are classified heterogeneous nanometer and answered
Condensation material includes the shell that the nanometer cupric silicate for the kernel and needle-like being made up of flake graphite alkene is constituted；Described needle-like is received
Rice cupric silicate is arranged on core surface in an array manner.
Further, kernel length and width of the present invention each stands alone as 2-6 μm, and thickness is 20-60nm.
Further, a diameter of 10-15nm of acicular nanometer cupric silicate of the present invention, length is 50-150nm.
Further, graphene@cupric silicates of the present invention are classified heterogeneous nano composite material and are prepared as follows：
1) surfactant, alcohols solvent are added in deionized water and forms mixed solution, then by graphene oxide point
It is dispersed in above-mentioned mixed solution, ultrasonic disperse is to obtain uniform suspension；
2) compound of silicate class is added in above-mentioned solution, be stirred at room temperature；After centrifugation, washing, drying, obtain
The graphene oxide of coated with silica；
3) take the graphene oxide of the coated with silica of step (2) acquisition scattered in deionized water, ultrasonic disperse；
The lower ammoniacal liquor regulation pH value that adds of stirring is added dropwise to 10-11.5, and by copper-containing compound, continues mixing suspension after stirring
It is transferred in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), room is cooled in atmosphere after being incubated at 120 DEG C~160 DEG C
Temperature, after centrifugation, washing, drying, obtains described graphene@cupric silicates and is classified heterogeneous nano composite material.
Further, graphene@cupric silicates of the present invention are classified heterogeneous nano composite material, specifically by the following method
Prepare：
1) surfactant, alcohols solvent are added in deionized water and forms mixed solution, then by graphene oxide point
It is dispersed in above-mentioned mixed solution, ultrasonic disperse 20-60min is to obtain uniform suspension；
2) compound of silicate class is added in above-mentioned solution, 5-8h is continuously stirred at room temperature；Through centrifugation, washing, do
After dry, the graphene oxide of coated with silica is obtained；The consumption of described compound of silicate class is with the matter of graphene oxide
Amount is calculated as 5~300mL/g；The compound of silicate class is methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester, positive silicic acid
Any of isopropyl ester, butyl silicate or two kinds；
3) take the graphene oxide of the coated with silica of step (2) acquisition scattered in deionized water, ultrasonic disperse 20-
60min；Add ammoniacal liquor regulation pH value under agitation to be added dropwise to 10-11.5, and by copper-containing compound, continuing will be mixed after stirring
Close suspension be transferred to liner be polytetrafluoroethylene (PTFE) stainless steel autoclave in, at 120 DEG C~160 DEG C be incubated 8~24h after
Room temperature is cooled in air, after centrifugation, washing, drying, described graphene@cupric silicates is obtained and is classified heterogeneous nano combined material
Material；The copper-containing compound is any of copper nitrate, copper acetate, copper chloride；The consumption of the copper-containing compound is to be taken
The quality of the graphene oxide of coated with silica is calculated as 0.005~0.05mol/g.
Further, surfactant of the present invention is cetyl trimethylammonium bromide, neopelex, ten
Any of dialkyl group trimethylammonium bromide or two kinds.
Further, alcohols solvent of the present invention is methanol, ethanol, propyl alcohol, isopropanol, n-butanol, glycerine, ring alcohol
Any of.
Generally, washing described in step (2) or (3) using any of deionized water, methanol, ethanol, isopropanol or
Two kinds are that cleaning solution is alternately washed.
The volumetric usage of alcohols solvent described in step (1) is calculated as 200~12000mL/ with the quality of graphene oxide
g；The consumption of the deionized water is calculated as 100~5000mL/g with the quality of graphene oxide；The surfactant and oxidation
The mass ratio of graphene is 1~5：1
The consumption of deionized water is calculated as 1 with the quality of the graphene oxide of taken coated with silica described in step (3)
~5L/g.
Further, the preparation method of the heterogeneous nano composite material of graphene@silicic acid ketone classification of the present invention is specifically grasped
Work is recommended as：
(1) by 0.05-0.5g surfactant, it is molten that 120ml alcohols solvents add the formation mixing of 10-50ml deionized waters
0.01-0.5g graphene oxides, are then dispersed in above-mentioned mixed solution by liquid, and ultrasonic disperse 20-60min is uniform to obtain
Suspension.
(2) 0.5-5ml esters of silicon acis is added in above-mentioned solution, 5-8h is continuously stirred at room temperature.Through centrifugation, washing, do
After dry, the graphene oxide of coated with silica is obtained.
(3) the graphene oxide 2-15mg of the coated with silica of step (2) acquisition is taken to be dispersed in 20-50ml deionized waters
In, ultrasonic disperse 20-60min.Ammoniacal liquor is added under gentle agitation and adjusts pH value to 10-11.5, and by 0.5-5ml 0.1mol/
L copper-containing compound is added dropwise, and it is the stainless of polytetrafluoroethylene (PTFE) to continue that mixing suspension is transferred into liner after stirring 5min
In steel autoclave, room temperature is cooled in atmosphere after 8~24h is incubated at 120 DEG C~160 DEG C.After centrifugation, washing, drying,
Obtain graphene@cupric silicates and be classified heterogeneous nano composite material.
Further, the present invention also provides described graphene@cupric silicates and is classified heterogeneous nano composite material as electrode material
The application of material.
The present invention has advantages below：
1. obtaining a kind of graphene@cupric silicates with core shell structure is classified heterogeneous nano composite material.2. institute of the present invention
Related products technique is simple, and reaction condition is gently easily realized and process repeatability can be good.3. obtained by graphene@cupric silicates
Heterogeneous nano composite material good dispersion is classified, specific surface area is big, it is expected in ultracapacitor, solar cell and sewage disposal
Huge applications are obtained Deng field.
Brief description of the drawings
Fig. 1 is that the graphene@cupric silicates with core shell structure prepared by the embodiment of the present invention 4 are classified heterogeneous nano combined material
The stereoscan photograph of material；
Fig. 2 is that the graphene@cupric silicates with core shell structure prepared by the embodiment of the present invention 4 are classified heterogeneous nano combined material
The transmission electron microscope photo of material；
Fig. 3 is that the graphene@cupric silicates with core shell structure prepared by the embodiment of the present invention 4 are classified heterogeneous nano combined material
XRD (X-ray diffraction) collection of illustrative plates of material；
Fig. 4 is that the graphene@cupric silicates with core shell structure prepared by the embodiment of the present invention 4 are classified heterogeneous nano combined material
The cyclic voltammetric collection of illustrative plates of material；
Embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
Embodiment 1
1) by 0.05g DTAB, it is molten that 120ml ethanol adds the formation mixing of 50ml deionized waters
0.01g graphene oxides, are then dispersed in above-mentioned mixed solution by liquid, and ultrasonic disperse 20min is to obtain uniform suspension.
2) 0.5ml tetraethyl orthosilicates are added in above-mentioned solution, 5h is continuously stirred at room temperature.Through centrifugation, ethanol and go
After ion water washing, drying, the graphene oxide of 0.012g coated with silica is obtained.
3) the graphene oxide 10mg that the silica for taking step (2) to obtain is coated is dispersed in 20ml deionized waters, ultrasound
Scattered 20min.Under gentle agitation add ammoniacal liquor regulation pH be 10 and by 0.5ml 0.1mol/L acetic acid copper compound dropwise
Add, continue to stir 5min, mixing suspension is transferred in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), at 120 DEG C
24h is incubated, room temperature is cooled in atmosphere, after centrifugation, ethanol and deionized water washing washing, drying, 7mg graphite is obtained
Alkene@cupric silicates are classified heterogeneous nano material, and the length and width of its kernel is about 2-6 μm, and thickness is about 20-60nm, acicular nanometer silicic acid
The diameter of copper is about 10nm, and length is about 50nm.
Embodiment 2
1) by 0.03g neopelex, 120ml propyl alcohol adds 30ml deionized waters formation mixed solution, so
0.01g graphene oxides are dispersed in above-mentioned mixed solution afterwards, ultrasonic disperse 40min is to obtain uniform suspension.
2) 3ml methyl silicates are added in above-mentioned solution, 6h is continuously stirred at room temperature.Through centrifugation, methanol and go from
After sub- water washing, drying, the graphene oxide of 0.015g coated with silica is obtained.
3) step 2 is taken) the graphene oxide 10mg of coated with silica that obtains is dispersed in 40ml deionized waters, ultrasound
Scattered 40min.Ammoniacal liquor regulation PH=10.8 is added under gentle agitation and by 0.6ml 0.1mol/L copper nitrate and 0.9ml
0.1mol/L copper acetates are added dropwise, and continue to stir 5min, and it is the stainless of polytetrafluoroethylene (PTFE) that mixing suspension is transferred into liner
In steel autoclave, 12h is incubated at 140 DEG C, room temperature is cooled in atmosphere, after centrifugation, washing, drying, obtain 7mg graphite
Alkene@cupric silicates are classified heterogeneous nano material, and the length and width of its kernel is about 2-6 μm, and thickness is about 20-60nm, acicular nanometer silicic acid
The diameter of copper is about 10nm, and length is about 80nm.
Embodiment 3
1) by 0.5g DTAB, it is molten that 120ml n-butanols add the formation mixing of 50ml deionized waters
0.5g graphene oxides, are then dispersed in above-mentioned mixed solution by liquid, and ultrasonic disperse 40min is to obtain uniform suspension.
2) the positive isopropyl silicates of 2.5ml are added in above-mentioned solution, 6h is continuously stirred at room temperature.Through centrifugation, washing, do
After dry, the graphene oxide of 1.8g coated with silica is obtained.
3) step 2 is taken) the graphene oxide 10mg of coated with silica that obtains is dispersed in 10ml deionized waters, ultrasound
Scattered 40min.Ammoniacal liquor regulation PH=10 is added under gentle agitation and by 3ml 0.1mol/L copper chloride and 2ml 0.1mol/
L copper acetates are added dropwise, and continue to stir 5min, and mixing suspension is transferred into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE)
In, 8h is incubated at 140 DEG C, room temperature is cooled in atmosphere, after centrifugation, isopropanol and deionized water washing, drying, is obtained
7mg graphene@cupric silicates are classified heterogeneous nano material, and the length and width of its kernel is about 2-6 μm, and thickness is about 20-60nm, pin
The diameter of shape nanometer cupric silicate is about 10nm, and length is about 10nm.
Embodiment 4
1) by 0.5g cetyl trimethylammonium bromide, it is molten that 120ml isopropanols add the formation mixing of 50ml deionized waters
0.2g graphene oxides, are then dispersed in above-mentioned mixed solution by liquid, and ultrasonic disperse 60min is to obtain uniform suspension.
2) 5ml butyl silicates are added in above-mentioned solution, 8h is continuously stirred at room temperature.Through centrifugation, absolute ethyl alcohol and
After deionized water washing, drying, the graphene oxide of 1.2g coated with silica is obtained.
3) step 2 is taken) the graphene oxide 10mg of coated with silica that obtains is dispersed in 50ml deionized waters, ultrasound
Scattered 60min.Under gentle agitation add ammoniacal liquor regulation pH be 11.5 and by 3ml 0.1mol/L acetic acid copper compound dropwise
Add, continue to stir 5min, mixing suspension is transferred in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), at 160 DEG C
24h is incubated, room temperature is cooled in atmosphere, after centrifugation, washing, drying, the graphene@cupric silicates classification for obtaining 7mg is heterogeneous
Nano material, the length and width of its kernel is about 2-6 μm, and thickness is about 20-60nm, and the diameter of acicular nanometer cupric silicate is about 15nm,
Length is about 150nm.
Fig. 1 is that the graphene@cupric silicates with core shell structure prepared by the embodiment of the present invention 4 are classified heterogeneous nano combined material
The stereoscan photograph of material；The two-sided of graphene can be observed from figure and grown more regular cupric silicate nano whiskers knot
Structure.Cupric silicate nanoneedle is erected at graphene film layer surface, and array structure is presented.Under high-amplification-factor, nanoneedle is in narrow rule
Very little distribution, nearly all in 15nm or so, the distance between adjacent nano pin is about 10-20nm.
Fig. 2 is that the graphene@cupric silicates with core shell structure prepared by the embodiment of the present invention 4 are classified heterogeneous nano combined material
The transmission electron microscope photo of material；As seen from the figure, graphene@cupric silicates lamella can preferably disperse.Graphene film layer surface is grown
More intensive nano needle arrays structure, and structure is more regular.It can be seen that the length of nanoneedle under high-amplification-factor
About 150nm.
Fig. 3 is that the graphene@cupric silicates with core shell structure prepared by the embodiment of the present invention 4 are classified heterogeneous nano combined material
XRD (X-ray diffraction) collection of illustrative plates of material；The constituent that nanoneedle is can confirm that from figure is cupric silicate.The width of these characteristics
Diffraction maximum is indexed to be understood to belong to cupric silicate (CuSiO3·2H2O, JCPDS card no.03-0219).Sample at 20.4 °,
26.54 °, 30.54 °, 31.84 °, 36.5 °, 56.4 °, 62.7 ° and 71.4 ° occur in that varying strength diffraction maximum, correspondence silicic acid
(130) of steel structure, (132), (023), (360) and (362) crystal face.
Embodiment 5
1) the graphene@cupric silicates for obtaining embodiment 4 are classified heterogeneous nano material and acetylene carbon black and carboxymethyl cellulose
Plain (CMC) is with 70:25:5 mass ratio mixing.30min is stirred, the slurry of certain viscosity is obtained.
2) take step 1) obtain slurry be coated uniformly on small glass bar on copper sheet, coated weight is about 1.5-2.0mg/
cm2, film surface is as far as possible smooth, and texture is tried one's best unanimously.
3) take step 2) obtain pole piece at 120 DEG C dry 2h, 6MPa pressure push 10s shaping.
4) take step 3) pole piece that obtains dries 1h under the conditions of 120 DEG C of vacuum drying chamber, weigh, after be put into vacuum drying
120 DEG C of case is dried overnight standby.
5) step 4 is taken) pole piece that obtains, in the feeding glove box such as battery case, barrier film, electrolyte, diaphragm seal, assembling electricity
Pond.
6) take step 5) obtain battery standing stay overnight after carry out electrochemistry experiment.By the battery folders of acquisition in battery carrier
On, the cyclic voltammetry of sample, scanning are carried out on electrochemical workstation RST4800 (Suzhou Rui Site Instrument Ltd.)
Speed is 0.1mv/s.
Fig. 4 is that the graphene cupric silicate with core shell structure obtained according to above-mentioned steps is classified heterogeneous nano combined material
The cyclic voltammetric collection of illustrative plates of material；It can be observed from figure, do not show substantially decay in 5 cyclic voltammetries, illustrate sample
Product cyclical stability is preferable.
Claims (10)
1. a kind of graphene@cupric silicates are classified heterogeneous nano composite material, it is characterised in that：The graphene@cupric silicates classification
Heterogeneous nano composite material includes the shell that the nanometer cupric silicate for the kernel and needle-like being made up of flake graphite alkene is constituted；It is described
The nanometer cupric silicate of needle-like be arranged in an array manner on core surface.
2. graphene@cupric silicates as claimed in claim 1 are classified heterogeneous nano composite material, it is characterised in that：Described is interior
Core length and width each stands alone as 2-6 μm, and thickness is 20-60nm；A diameter of 10-15nm of described acicular nanometer cupric silicate, length
For 50-150nm.
3. graphene@cupric silicates as claimed in claim 1 are classified heterogeneous nano composite material, it is characterised in that the graphite
Alkene@cupric silicates are classified heterogeneous nano composite material and are prepared as follows：
1) surfactant, alcohols solvent are added in deionized water and forms mixed solution, be then dispersed in graphene oxide
In above-mentioned mixed solution, ultrasonic disperse is to obtain uniform suspension；
2) compound of silicate class is added in above-mentioned solution, be stirred at room temperature；After centrifugation, washing, drying, dioxy is obtained
The graphene oxide of SiClx cladding；
3) take the graphene oxide of the coated with silica of step (2) acquisition scattered in deionized water, ultrasonic disperse；In stirring
Lower addition ammoniacal liquor regulation pH value is added dropwise to 10-11.5, and by copper-containing compound, continues to shift mixing suspension after stirring
To liner in the stainless steel autoclave of polytetrafluoroethylene (PTFE), room temperature is cooled in atmosphere after being incubated at 120 DEG C~160 DEG C,
After centrifugation, washing, drying, obtain described graphene@cupric silicates and be classified heterogeneous nano composite material.
4. a kind of graphene@cupric silicates as claimed in claim 1 are classified the preparation method of heterogeneous nano composite material, its feature
It is that methods described is：
1) surfactant, alcohols solvent are added in deionized water and forms mixed solution, be then dispersed in graphene oxide
In above-mentioned mixed solution, ultrasonic disperse 20-60min is to obtain uniform suspension；
2) compound of silicate class is added in above-mentioned solution, 5-8h is continuously stirred at room temperature；After centrifugation, washing, drying,
Obtain the graphene oxide of coated with silica；The consumption of described compound of silicate class is calculated as with the quality of graphene oxide
5~300mL/g；The compound of silicate class is methyl silicate, tetraethyl orthosilicate, positive isopropyl silicate, butyl silicate
Any of or two kinds；
3) take the graphene oxide of the coated with silica of step (2) acquisition scattered in deionized water, ultrasonic disperse 20-
60min；Add ammoniacal liquor regulation pH value under agitation to be added dropwise to 10-11.5, and by copper-containing compound, continuing will be mixed after stirring
Close suspension be transferred to liner be polytetrafluoroethylene (PTFE) stainless steel autoclave in, at 120 DEG C~160 DEG C be incubated 8~24h after
Room temperature is cooled in air, after centrifugation, washing, drying, described graphene@cupric silicates is obtained and is classified heterogeneous nano combined material
Material；The copper-containing compound is any of copper nitrate, copper acetate, copper chloride；The consumption of the copper-containing compound is to be taken
The quality of the graphene oxide of coated with silica is calculated as 0.005~0.05mol/g.
5. method as claimed in claim 4, it is characterised in that：The surfactant be cetyl trimethylammonium bromide,
Any of neopelex, DTAB or two kinds.
6. method as claimed in claim 4, it is characterised in that：The alcohols solvent is methanol, ethanol, propyl alcohol, isopropanol, just
Any of butanol.
7. method as claimed in claim 4, it is characterised in that：Washing is using deionized water, first described in step (2) or (3)
Any of alcohol, ethanol, isopropanol or two kinds are that cleaning solution is alternately washed.
8. method as claimed in claim 4, it is characterised in that：The volumetric usage of alcohols solvent described in step (1) is with oxygen
The quality of graphite alkene is calculated as 200~12000mL/g；The consumption of the deionized water is calculated as 100 with the quality of graphene oxide
~5000mL/g；The consumption of the surfactant and the mass ratio of graphene oxide are 1~5：1.
9. method as claimed in claim 4, it is characterised in that：The consumption of deionized water is with taken dioxy described in step (3)
The quality of the graphene oxide of SiClx cladding is calculated as 1~5L/g.
10. a kind of graphene@cupric silicates as claimed in claim 1 are classified heterogeneous nano composite material answering as electrode material
With.
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