CN106745202A - A kind of SnO2The preparation method of/Graphene composite hollow ball - Google Patents
A kind of SnO2The preparation method of/Graphene composite hollow ball Download PDFInfo
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- CN106745202A CN106745202A CN201710043190.9A CN201710043190A CN106745202A CN 106745202 A CN106745202 A CN 106745202A CN 201710043190 A CN201710043190 A CN 201710043190A CN 106745202 A CN106745202 A CN 106745202A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 4
- 210000001951 dura mater Anatomy 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000011261 inert gas Substances 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 125000005456 glyceride group Chemical group 0.000 claims description 3
- 239000000787 lecithin Substances 0.000 claims description 3
- 229940067606 lecithin Drugs 0.000 claims description 3
- 235000010445 lecithin Nutrition 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 3
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229950008882 polysorbate Drugs 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- SSDDBKANEGGSRG-UHFFFAOYSA-N thiophene;tin Chemical compound [Sn].C=1C=CSC=1 SSDDBKANEGGSRG-UHFFFAOYSA-N 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000008602 contraction Effects 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000004044 response Effects 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XPDXVDYUQZHFPV-UHFFFAOYSA-N Dansyl Chloride Chemical compound C1=CC=C2C(N(C)C)=CC=CC2=C1S(Cl)(=O)=O XPDXVDYUQZHFPV-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention discloses a kind of SnO2The preparation method of/Graphene composite hollow ball, described SnO2The preparation method of/Graphene composite hollow ball is the method and the compound realization of the step of chemical vapour deposition technique two using dura mater version Hydrothermal Synthesiss, is the size and pattern that composite hollow ball is effectively controlled using template.Synthesize SnO first by the way of Hydrothermal Synthesiss2/ Graphene composite hollow ball electrode material.The present invention is by building SnO2/ Graphene composite hollow ball, greatly lifts the performances such as contact area and the absorption of material.In charge and discharge process, Graphene mechanical tenacity is adapted to the volumetric expansion and contraction of material, is capable of the complete of holding electrode.SnO in the basic conditions2CV and charge and discharge electrical property of/the Graphene composite hollow ball on foam nickel electrode.SnO2The specific capacitance of/Graphene composite hollow ball can reach 43.30Fg‑1, with fabulous discharge and recharge behavior.The raw material that the present invention is used is cheap, it is easy to operate, and equipment is simple, be easy to industrialized production.
Description
Technical field
The invention belongs to electrochemical function field of material technology, and in particular to a kind of SnO2/ Graphene composite hollow ball
Preparation method.
Background technology
SnO2As typical type n semiconductor material, to lithium ion battery discharge and recharge, solar energy storage, gas sensitive,
Photoelectrocatalysis reaction is all widely used.Difference according to its pattern, size, crystal formation, thing phase is applied to different field.SnO2
Material has various geometrical morphology, spherical, octahedra, sheet, flower pattern, banding pattern etc..In numerous patterns, ball shaped nano grain
Sub- crystallization degree is high to be conducive to photoelectrocatalysis to react, and colloidal attitude is more stable in aqueous, and specific surface area is also above other patterns.
So SnO2Spherical and derivative hollow, hollow composite structure is widely paid close attention to.
Each carbon atom of Graphene is sp2Hydridization, and contribute a remaining p orbital electron to form big pi-electron can be with
Move freely, assign Graphene excellent electric conductivity, the class aromatic hydrocarbon benzene ring structure of its stabilization has the electron transfer of superelevation
Rate, mobility is up to 2*105cm2/ (Vs), 140 times of electron mobility about in silicon, wherein electrical conductivity is up to 106S/m.It is super
Big specific surface area, excellent mechanics and thermal property.Area is 1m2Graphene synusia can bear the quality of 4kg.Graphite
Alkene can have potential application value as a kind of typical two dimension enhancing phase in field of compound material.
Nucleocapsid micro Nano material, wide variety, selectivity is big, the premium properties of different nano materials can be superimposed
Come, play the effect of double optimization.Thus, nano core-shell composite construction has extremely wide application prospect.Micro-nano nucleocapsid
Material combines the bioaffinity energy of specific nano-particle due to its small size, in medical bioengineering, as medicine
Carrier has started the upsurge of domestic and international research by extensive concern.In terms of the energy, the scalability of core-shell material, elasticity is special
Photoelectric properties be can replace the energy development bring hope.Nanometer nuclear shell nano-structure and hollow structure opposing solid particle have more
Good catalysis activity, the advantage such as its high-specific surface area, low-density, low quality, cheap turns into potential cell electrode catalyst
Material.
The content of the invention
It is an object of the invention to provide a kind of SnO2The preparation method of/Graphene composite hollow ball.
The object of the present invention is achieved like this, described SnO2The preparation method of/Graphene composite hollow ball is to use
The method of dura mater version Hydrothermal Synthesiss is compound with the step of chemical vapour deposition technique two to be realized, is specifically included：
A, surfactant will be added in high molecular polymerization microballoon ultrasonic disperse to solution, then that Sn presomas are added dropwise is water-soluble
Liquid, reacts 3~8h at room temperature, and centrifugation is washed 2~4 times, is dried to obtain white powder a, then enters white powder a
Row calcining obtains pale powder b；
B, preparation carbon source, pale powder b is put into the heating zone center of electric furnace, and enclosed reaction chamber is passed through inert gas,
To 700~1000 DEG C, holding inert gas flow is 50~100ml/min to heating response room temperature, is incubated 60~240min, is entered
The treatment of row high temperature preheating obtains black powder, i.e. object SnO2/ Graphene composite hollow ball.
The present invention is by building SnO2/ Graphene composite hollow ball, greatly lifts contact area and absorption of material etc.
Performance.In charge and discharge process, Graphene mechanical tenacity is adapted to the volumetric expansion and contraction of material, is capable of holding electrode
Completely.SnO in the basic conditions2CV and charge and discharge electrical property of/the Graphene composite hollow ball on foam nickel electrode.SnO2/ graphite
The specific capacitance of alkene composite hollow ball can reach 43.30Fg-1, with fabulous discharge and recharge behavior.
The present invention is the size and pattern that composite hollow ball is effectively controlled using template.It is first by the way of Hydrothermal Synthesiss
Secondary synthesis SnO2/ Graphene composite hollow ball electrode material.The raw material that the present invention is used is cheap, it is easy to operate, and equipment letter
Singly, it is easy to industrialized production.
Advantages of the present invention：
1st, the raw material that preparation scheme of the present invention is used is simple, and product is single, easily separated purification.Preparation method is used
Two-step method, reaction condition is gentle, easy to operate controllable.Required high pressure, vacuum activating equipment are simple, it is easy to mass produce.
2nd, by SnO2/ Graphene compound action, considerably increases SnO2Conductive capability.
Brief description of the drawings
Fig. 1 is SnO prepared by embodiment 12/ Graphene composite hollow ball and the SnO not met2Micro-nano hollow ball is not
CV with sweep speed schemes；
Wherein, A is SnO2Micro-nano hollow ball；B is SnO2/ Graphene composite hollow ball；
Fig. 2 is SnO prepared by embodiment 12/ Graphene composite hollow ball and the SnO not met2Micro-nano hollow ball is not
With the CV figure electrode specific capacitances of sweep speed with sweep speed change curve；
Wherein, a is SnO2Micro-nano hollow ball；B is SnO2/ Graphene composite hollow ball.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is further illustrated, but the present invention is subject to never in any form
Limitation, based on present invention teach that any conversion or replacement made, belong to protection scope of the present invention.
SnO of the present invention2The preparation method of/Graphene composite hollow ball is the method using dura mater version Hydrothermal Synthesiss
It is compound with the step of chemical vapour deposition technique two to realize, specifically include：
A, surfactant will be added in high molecular polymerization microballoon ultrasonic disperse to solution, then that Sn presomas are added dropwise is water-soluble
Liquid, reacts 3~8h at room temperature, and centrifugation is washed 2~4 times, is dried to obtain white powder a, then enters white powder a
Row calcining obtains pale powder b；
B, preparation carbon source, pale powder b is put into the heating zone center of electric furnace, and enclosed reaction chamber is passed through inert gas,
To 700~1000 DEG C, holding inert gas flow is 50~100ml/min to heating response room temperature, is incubated 60~240min, is entered
The treatment of row high temperature preheating obtains black powder, i.e. object SnO2/ Graphene composite hollow ball.
High molecular polymerization microballoon described in step A is poly (methyl methacrylate) micro-sphere, polystyrene microsphere, polyethylene
One or more in pyrrolidones microballoon, dansyl chloride allylamine microballoon and sulfonated polyethylene microballoon.
Solution described in step A is one or more in water, ethanol, propyl alcohol and acetonitrile.
Described surfactant is stearic acid, neopelex, lecithin, fatty glyceride, aliphatic acid
One or more in sorb and polysorbate.
Sn presomas described in step A are SnCl2、SnSO4、Sn(NO3)2, tributyl tin, the one of thiophene tin trimethyl
Plant or various.
Centrifugation described in step A is 2~4min of centrifugation under rotating speed 5000rpm/min.
Drying described in step A is vacuum drying, and drying temperature is 50~70 DEG C, and drying time is 2~8h.
Calcining described in step A is calcined in Muffle furnace, and 300 DEG C are risen to from room temperature with the heating rate of 2 DEG C/min,
And it is incubated 2~6h at 300 DEG C.
Carbon source described in step B is one or more in sucrose solution, chromatographically pure ethanol solution, methanol solution.
High temperature pretreatment described in step B is to open delicate flow pump so that reaction solution injects anti-by capillary
Room is answered, solution feed speed is 20 microlitres/min, and the reaction time is 5-10min；Reaction is finished, feed-disabling reaction solution, is closed
Electric furnace is closed, inert gas flow 100mL/min is kept, until furnace temperature is cooled to less than 300 DEG C, black powder is obtained.
Described inert gas is argon gas.
SnO of the present invention2The preparation method concrete operations of/Graphene composite hollow ball are as follows：
One step：(1) the high molecular polymerization microballoon ultrasonic disperse of different nano-scales to water, ethanol, propyl alcohol, acetonitrile is chosen
In one or several mixed solution；(2) surfactant is added；(3) the Sn precursor aqueous solution is slowly added dropwise, at room temperature,
Reaction 3-8h；(4) after reaction stops, by end-product centrifugation, 5000rpm, 3min；Washed 3 times with water and ethanol respectively；
(5) 60 DEG C of vacuum drying 2-8h.White powder is obtained after drying；(6) white powder that will be prepared is placed in Muffle furnace and calcines,
With 2 DEG C of min-1Heating rate rise to 300 DEG C from room temperature, 300 DEG C keep 2-6h, obtain pale powder.
Two steps：(1) the heating zone center that the pale powder of one step is put into carbon source electric furnace, enclosed reaction chamber are prepared as；
(2) inert reaction gas is passed through, flow is 50-200mL/min, and heating response room temperature is to 1000 DEG C.(3) inert reaction is kept
Gas flow is constant, insulation a period of time, high temperature preheating treatment is carried out to grey powder；(4) delicate flow pump is opened so that anti-
Solution is answered to inject reative cell by capillary, solution feed speed is 20 microlitres/min, and the reaction time is 5-10min；(5) react
Finish, feed-disabling reaction solution, close electric furnace, inert gas flow 100mL/min is kept, until furnace temperature is cooled to 300 DEG C
Hereinafter, black powder is obtained.
So that case is embodied, the present invention will be further described below：
Embodiment 1
The polystyrene microsphere ultrasonic disperse of 300nm is chosen in ethanol；Add 0.025g PVP (10mL H2O) surface
Activating agent；It is slowly added dropwise 0.05molL-1SnSO4, the 10mL aqueous solution, at room temperature, react 3h；After reaction stops, by end-product
Centrifugation, 5000rpm, 3min；Washed 3 times with water and ethanol respectively；60 DEG C of vacuum drying 2h.White powder is obtained after drying
End；The white powder that will be prepared is placed in Muffle furnace and calcines, with 2 DEG C of min-1Heating rate rise to 300 DEG C from room temperature,
300 DEG C of holding 2h, obtain pale powder.White powder is placed in Muffle furnace and is calcined, with 2 DEG C of min-1Heating rate from room
Temperature rise keeps 2h to 400 DEG C at 400 DEG C, obtains pale powder.
With ethanol as carbon source, the pale powder of a step is put into the heating zone center of electric furnace, enclosed reaction chamber；It is passed through argon
Gas, flow is 50mL/min, and heating response room temperature is to 700 DEG C.Insulation a period of time, high temperature preheating is carried out to pale powder
Treatment；Open delicate flow pump so that reaction solution by capillary inject reative cell, solution feed speed for 30 microlitres/
Min, the reaction time is 7min；Reaction is finished, feed-disabling reaction solution, closes electric furnace, keeps inert gas flow 100mL/
Min, until furnace temperature is cooled to less than 300 DEG C, obtains black powder.
Embodiment 2
The polyvinylpyrrolidone microballoon ultrasonic disperse of 300nm is chosen in ethanol；Add 0.020g fatty glycerides
Surfactant；It is slowly added dropwise 0.03molL-1SnCl2, the 10mL aqueous solution, at room temperature, react 4h；After reaction stops, will eventually
Product centrifugation, 5000rpm, 3min；Washed 3 times with water and ethanol respectively；60 DEG C of vacuum drying 2h.White is obtained after drying
Powder；The white powder that will be prepared is placed in Muffle furnace and calcines, with 2 DEG C of min-1Heating rate rise to 300 DEG C from room temperature,
2h is kept at 300 DEG C, pale powder is obtained.White powder is placed in Muffle furnace and is calcined, with 2 DEG C of min-1Heating rate from
Room temperature rises to 600 DEG C, and 2h is kept at 600 DEG C, obtains pale powder.
With propyl alcohol as carbon source, the pale powder of a step is put into the heating zone center of electric furnace, enclosed reaction chamber；It is passed through argon
Gas, flow is 100mL/min, and heating response room temperature is to 800 DEG C.Insulation a period of time, high temperature is carried out to pale powder pre-
Heat treatment；Open delicate flow pump so that reaction solution by capillary inject reative cell, solution feed speed for 40 microlitres/
Min, the reaction time is 15min；Reaction is finished, feed-disabling reaction solution, closes electric furnace, keeps inert gas flow 150mL/
Min, until furnace temperature is cooled to less than 200 DEG C, obtains black powder.
Embodiment 3
The sulfonated polyethylene microballoon ultrasonic disperse of 300nm is chosen in ethanol；Add 0.040g lecithin surfactants；
It is slowly added dropwise 0.06molL-1Tributyl tin, at room temperature, reacts 5h；After reaction stops, by end-product centrifugation,
5000rpm,3min；Washed 3 times with water and ethanol respectively；60 DEG C of vacuum drying 2h.White powder is obtained after drying；To prepare
White powder be placed in Muffle furnace calcine, with 2 DEG C of min-1Heating rate rise to 300 DEG C from room temperature, 300 DEG C holding
2h, obtains pale powder.White powder is placed in Muffle furnace and is calcined, with 2 DEG C of min-1Heating rate rise to 800 from room temperature
DEG C, 2h is kept at 800 DEG C, obtain pale powder.
With glucose as carbon source, the pale powder of a step is put into the heating zone center of electric furnace, enclosed reaction chamber；It is passed through
Argon gas, flow is 60mL/min, and heating response room temperature is to 1000 DEG C.Insulation a period of time, high temperature is carried out to pale powder
The pre-heat treatment；Open delicate flow pump so that reaction solution injects reative cell by capillary, solution feed speed is 35 micro-
Liter/min, the reaction time is 12min；Reaction is finished, feed-disabling reaction solution, closes electric furnace, keeps inert gas flow
80mL/min, until furnace temperature is cooled to less than 400 DEG C, obtains black powder.
SnO prepared by the present invention of embodiment 42The electrocatalysis characteristic of/Graphene composite hollow ball
Electrochemical property test
The test of cyclic voltammetric (CV), cyclic voltammetric potential range is -1-0V.The test of electrochemical properties passes through three electrodes
System is carried out at room temperature, platinum filament, and Ag/AgCl electrodes are respectively to electrode and reference electrode.
Contrasted according to cyclic voltammetry curve, SnO2(CV) graphical trend of/Graphene composite hollow ball and discharge time are bright
It is aobvious to be better than SnO2Micro-nano hollow ball.The potential range of -1-0V, measures SnO in 1M KOH solutions2/ Graphene composite hollow ball
Maximum specific capacitance be 43.30Fg-1.The specific capacitance of electrode is gradually reduced with the increase of sweep speed, SnO2/ graphite
The specific capacitance of alkene composite hollow ball electrode is all higher than SnO under different scanning rates2The specific capacitance of micro-nano hollow ball electrode,
And the increase with sweep speed is presented stable decrease speed.As a probe material of electrode for capacitors, by contrast,
SnO2Electrode material has potential storing up electricity performance in terms of capacitor.
Claims (10)
1. a kind of SnO2The preparation method of/Graphene composite hollow ball, it is characterised in that described SnO2/ Graphene composite hollow
The preparation method of ball is the method and the compound realization of the step of chemical vapour deposition technique two using dura mater version Hydrothermal Synthesiss, is specifically included：
A, by high molecular polymerization microballoon ultrasonic disperse to solution, add surfactant, then Sn precursor water solutions are added dropwise, in
3~8h is reacted at room temperature, and centrifugation is washed 2~4 times, is dried to obtain white powder a, is then calcined white powder a
Obtain pale powder b；
B, preparation carbon source, pale powder b is put into the heating zone center of electric furnace, and enclosed reaction chamber is passed through inert gas, heats
To 700~1000 DEG C, holding inert gas flow is 50~100ml/min to reaction chamber temperature, is incubated 60~240min, carries out height
Warm the pre-heat treatment obtains black powder, i.e. object SnO2/ Graphene composite hollow ball.
2. SnO according to claim 12The preparation method of/Graphene composite hollow ball, it is characterised in that described in step A
High molecular polymerization microballoon be poly (methyl methacrylate) micro-sphere, polystyrene microsphere, polyvinylpyrrolidone microballoon, red sulphonyl
One or more in chlorallyl amine microballoon and sulfonated polyethylene microballoon.
3. SnO according to claim 12The preparation method of/Graphene composite hollow ball, it is characterised in that described in step A
Solution be one or more in water, ethanol, propyl alcohol and acetonitrile.
4. SnO according to claim 12The preparation method of/Graphene composite hollow ball, it is characterised in that described surface
Activating agent is in stearic acid, neopelex, lecithin, fatty glyceride, aliphatic acid sorb and polysorbate
One or more.
5. SnO according to claim 12The preparation method of/Graphene composite hollow ball, it is characterised in that described in step A
Sn presomas be SnCl2、SnSO4、Sn(NO3)2, tributyl tin, thiophene tin trimethyl one or more.
6. SnO according to claim 12The preparation method of/Graphene composite hollow ball, it is characterised in that described in step A
Centrifugation be under rotating speed 5000rpm/min centrifugation 2~4min.
7. SnO according to claim 12The preparation method of/Graphene composite hollow ball, it is characterised in that described in step A
Drying be vacuum drying, drying temperature be 50~70 DEG C, drying time be 2~8h.
8. SnO according to claim 12The preparation method of/Graphene composite hollow ball, it is characterised in that described in step A
Calcining be to be calcined in Muffle furnace, rise to 300 DEG C from room temperature with the heating rate of 2 DEG C/min, and 2~6h are incubated at 300 DEG C.
9. SnO according to claim 12The preparation method of/Graphene composite hollow ball, it is characterised in that described in step B
Carbon source be one or more in sucrose solution, chromatographically pure ethanol solution, methanol solution.
10. SnO according to claim 12The preparation method of/Graphene composite hollow ball, it is characterised in that institute in step B
The high temperature pretreatment stated is to open delicate flow pump so that reaction solution injects reative cell, solution feed speed by capillary
It is 20 microlitres/min, the reaction time is 5-10min；Reaction is finished, feed-disabling reaction solution, closes electric furnace, keeps indifferent gas
Body flow 100mL/min, until furnace temperature is cooled to less than 300 DEG C, obtains black powder.
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| CN113666365A (en) * | 2021-09-30 | 2021-11-19 | 萝北奥星新材料有限公司 | Method for preparing single-layer continuous graphene film by using hydrocarbon organic compound |
| CN113793914A (en) * | 2021-09-10 | 2021-12-14 | 陕西科技大学 | Reduced graphene oxide coated CNTs/SnO with hollow structure2Composite film and preparation method and application thereof |
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| CN106299309A (en) * | 2016-09-30 | 2017-01-04 | 上海交通大学 | Graphene half cladding tin oxide nano particles cluster composite material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113793914A (en) * | 2021-09-10 | 2021-12-14 | 陕西科技大学 | Reduced graphene oxide coated CNTs/SnO with hollow structure2Composite film and preparation method and application thereof |
| CN113793914B (en) * | 2021-09-10 | 2023-02-14 | 陕西科技大学 | Reduced graphene oxide coated CNTs/SnO with hollow structure 2 Composite film and preparation method and application thereof |
| CN113666365A (en) * | 2021-09-30 | 2021-11-19 | 萝北奥星新材料有限公司 | Method for preparing single-layer continuous graphene film by using hydrocarbon organic compound |
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