CN103035916B - Preparation method of a kind of nano-stannic oxide-graphene composite material and products thereof - Google Patents
Preparation method of a kind of nano-stannic oxide-graphene composite material and products thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 230000008569 process Effects 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 238000000967 suction filtration Methods 0.000 claims abstract description 19
- 125000003963 dichloro group Chemical group Cl* 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims description 29
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 27
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 9
- 239000007772 electrode material Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000006479 redox reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000006260 foam Substances 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000004044 response Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000005669 field effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 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
- 241000446313 Lamella Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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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
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- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of method for the preparation of nano-stannic oxide-graphene composite material, comprise: (a) successively adds graphene oxide and the sub-tin of dichloro and mix and blend in deionized water, charge ratio controls as in every 100ml deionized water, the mass ratio of graphene oxide and the sub-tin of dichloro is 57 ~ 374mg:10 ~ 24mg, obtains the mixed solution of graphene oxide-tin ash presoma thus; B (), by this mixed solution ultrasonic reaction at a certain temperature, ultrasonic power is set to 100 ~ 300W; C () performs suction filtration and cleaning to the suspension obtained through ultrasonic process, thus obtained composite products.The invention also discloses corresponding composite products and main application thereof.By the present invention, effectively can avoid the pollution to environment in production process, reduce production cost and energy consumption, and contribute to improving reaction efficiency and making course of reaction more abundant, and obtained composite products shows better combination property.
Description
Technical field
The invention belongs to Nano-composite materials field, more specifically, relate to preparation method of a kind of nano-stannic oxide-graphene composite material and products thereof.
Background technology
Graphene is carbon atom with the tightly packed cellular Colloidal particles carbon nanomaterial of sp2 hybrid systems, and it has good electricity, mechanics and thermal property, is the energy storage material of current great potential.Graphene-based composite material refers to and utilizes surface modifier, conducting polymer or transition metal oxide particle etc., the composite material obtained after finishing being carried out to Graphene by surface reaction, its abundance also embodies good performance index, is the electrode material of the element first-selections such as ultracapacitor.Research shows, by possessing positive tetrahedron Rutile structure, tin ash that physicochemical properties are stable is evenly attached to the hardness that composite material that Graphene particle surface forms can significantly improve material, and strengthen the performance such as electrochemistry capacitance, conductance, therefore obtain in multiple fields such as ultracapacitor, information material, lithium ion battery, solar cell and fuel cells and apply more and more widely.
Method for the preparation of tin ash-graphene composite material of the prior art such as comprises a kind of flower-like tin dioxide disclosed in CN102324502A and the preparation method of graphene composite material, wherein utilize hydro thermal method with stannic chloride pentahydrate, NaOH and graphene oxide for raw material, water is solvent, stir and carry out hydro-thermal reaction after 60 minutes, generate tin ash and graphene composite material thus.And for example disclose a kind of tin oxide/graphene nanometer composite and its preparation method and application in CN101927979A, the method with stannic chloride pentahydrate or two hydration stannous chloride, NaOH and graphene oxide for raw material, methyl-sulfoxide is solvent, stir and carry out hydro-thermal reaction after 2.5 hours, generate tin ash and graphene composite material.The defect of above-mentioned preparation method is mainly: (1) employs the materials such as alkaline NaOH or methyl-sulfoxide in preparation process, is unfavorable for environmental protection and increases production cost; (2) hydro-thermal reaction needs the high-temperature heating of long period, and energy consumption is high and production efficiency is on the low side.
In addition; also the preparation method of a kind of tin ash or metallic tin and graphene sheet layer composite material is disclosed in CN102255072A; after wherein organic solvent, the graphene oxide lamella hydrosol being mixed with pink salt; 0.5-12h is heated at 60-200 DEG C; obtain solid matter; gained solid matter is heated 0.5-10h under inert gas shielding at the temperature of 400-700 DEG C, thus obtained tin ash and graphene sheet layer composite material.The defect of the method is mainly: (1) in preparation process equally with an organic solvent, it is unfavorable for environmental protection and adds production cost; (2) owing to needing to react under higher reaction temperature condition, energy consumption is higher and stricter to equipment requirement; (3) whole reaction will be carried out under inert gas shielding, the corresponding requirement that improve production control aspect, and further increases manufacturing cost.Therefore, there is the technical need preparation method of tin ash-graphene composite material being made to improvement further in the related art.
Summary of the invention
For above defect and/or the technical need of prior art, the object of the present invention is to provide preparation method of a kind of nano-stannic oxide-graphene composite material and products thereof, it is by the research of key reaction thing and reaction condition thereof and improvement, environmental protection can be beneficial to, be convenient to quality control and high efficiency mode to prepare tin ash-graphene composite material product, and the product stannic oxide particle average diameter obtained by it is 5-8nm and is uniformly distributed in graphenic surface, and electric capacity is up to more than 120F/g, possesses better cycle performance simultaneously.
According to one aspect of the present invention, provide a kind of method for the preparation of nano-stannic oxide-graphene composite material, it is characterized in that, the method comprises the following steps:
A () take deionized water as solvent, successively add as the graphene oxide of solute and the sub-tin of dichloro and perform mix and blend, charge ratio controls as in every 100ml deionized water, the mass ratio of graphene oxide and the sub-tin of dichloro is 57 ~ 374mg:10 ~ 24mg, obtains the mixed solution of graphene oxide-tin ash presoma thus;
B (), by obtained mixed solution ultrasonic reaction 1 ~ 2 hour at the temperature of 25 DEG C ~ 40 DEG C, ultrasonic power is set to 100 ~ 300W;
C () performs suction filtration process to processing the suspension obtained through step (b), and the filter cake obtained after adopting the process of washed with de-ionized water suction filtration, thus obtained nano-stannic oxide-graphene composite material product in chondritic.
By above design, perform oxidation-reduction reaction, Sn in course of reaction owing to adopting graphene oxide and the sub-tin of dichloro as the crucial thing of reaction
2+first oxidized Graphene be adsorbed on its surface and be oxidized by it, meanwhile graphene oxide is reduced into Graphene, the stannic oxide particle of nanometer scale is fixed with like this in graphenic surface absorption, thus obtained required tin ash=graphene composite material product.This course of reaction compared with prior art, can effectively be avoided using organic substance environment being existed to pollution, and reduce production cost and also improve reaction efficiency, and the stannic oxide particle being adsorbed on graphenic surface is evenly distributed, its average-size is about 5-8nm; In addition, owing to adopting ultrasonic wave process, can reaction efficiency be improved compared with the hydro-thermal reaction of prior art, and it is more abundant that whole course of reaction is carried out, be conducive to reduction efficiency, and stannic oxide particle obtains and distributes more uniformly on graphenic surface.
As further preferably, after step (c), the freeze drying process of 12 ~ 72 hours can also be performed to the solid obtained after washed with de-ionized water.
According to another aspect of the present invention, additionally provide corresponding nano-stannic oxide-graphene composite material product.
As further preferably, in described composite products, the average diameter of particles of nano-stannic oxide is about 5-8nm.
According to another aspect of the present invention, additionally provide the purposes of prepared nano-stannic oxide-graphene composite material product in for example ultracapacitor, field-effect transistor, lithium ion battery or fuel cell etc.
In general, according to nano-stannic oxide-graphene composite material of the present invention preparation method and products thereof compared with prior art, mainly possess following technological merit:
1, by adopting graphene oxide and the sub-tin of dichloro as the crucial thing of reaction and preparing tin ash-graphene composite material by ultrasonic reaction mode, effectively can avoid using and the organic substance polluted is existed to environment, reduce production cost and energy consumption, contribute to improving reaction efficiency simultaneously, and make course of reaction more abundant;
2, by selecting aspects such as the charge ratio in course of reaction, response parameters, can form the stannic oxide particle of nanometer scale at graphenic surface and be evenly distributed, obtained composite products shows better combination property;
3, overall preparation method's economy, environmental protection, and be convenient to quality control, and can be used for large-scale industrialization batch production, be therefore particularly useful for making the purposes such as ultracapacitor, lithium ion battery negative, fuel cell electrode or field-effect transistor.
Accompanying drawing explanation
Fig. 1 is according to the method flow diagram of the present invention for the preparation of nano-stannic oxide-graphene composite material;
Fig. 2 a is the transmission electron microscope photo according to the nano-stannic oxide obtained by the embodiment of the present invention 1-graphene composite material product;
Fig. 2 b is according to the nano-stannic oxide obtained by the embodiment of the present invention 1-cyclic voltammetry curve of graphene composite material product under difference sweeps speed;
Fig. 2 c is according to the constant current charge-discharge curve chart of the nano-stannic oxide obtained by the embodiment of the present invention 1-graphene composite material product under 1mA/mg current density;
Fig. 2 d is according to the constant current charge-discharge curve chart of the nano-stannic oxide obtained by the embodiment of the present invention 1-graphene composite material product under 2mA/mg current density;
Fig. 2 e is the X ray diffracting spectrum according to the nano-stannic oxide obtained by the embodiment of the present invention 1-graphene composite material product.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Fig. 1 is according to the method flow diagram of the present invention for the preparation of nano-stannic oxide-graphene composite material.As shown in fig. 1, in order to prepare tin ash-graphene composite material product, first, take deionized water as solvent, successively add as the graphene oxide of solute and the sub-tin of dichloro and perform mix and blend, wherein charge ratio controls as in every 100ml deionized water, and the mass ratio of graphene oxide and the sub-tin of dichloro is 57 ~ 374mg:10 ~ 24mg, obtains the mixed solution of graphene oxide-tin ash presoma thus; Then, by obtained mixed solution ultrasonic reaction 1 ~ 2 hour at the temperature of 25 DEG C ~ 40 DEG C, ultrasonic power is set to 100 ~ 300W; Finally, suction filtration process is performed to the suspension obtained through ultrasonic process, and the filter cake obtained after adopting the process of washed with de-ionized water suction filtration, thus obtained nano-stannic oxide-graphene composite material product in chondritic.After this composite products obtained, the freeze drying process of 12-72 hour can also be performed to this solid.
Embodiment 1
Deionized water 80ml is added as solvent in reaction vessel, the sub-tin of dichloro of the graphene oxide and 18.7mg that then successively add 106.7mg is wherein as solute, then mix and blend about 1 minute, obtains the mixed solution of graphene oxide and tin ash predecessor thus;
Then, by this mixed solution 25 DEG C, ultrasonic power performs ultrasonic response 1.5 hours under being the condition of 120W;
Then, suction filtration process is performed to the suspension obtained through ultrasonic process, and obtain after adopting the process of washed with de-ionized water suction filtration include tin ash-Graphene at interior filter cake, finally by obtained solid freeze drying process 12 hours, obtained basic nano-stannic oxide-graphene composite material product in chondritic thus.
Embodiment 2
Deionized water 100ml is added as solvent in reaction vessel, the sub-tin of dichloro of the graphene oxide and 10mg that then successively add 160mg is wherein as solute, then mix and blend 60 minutes, obtains the mixed solution of graphene oxide and tin ash predecessor thus;
Then, by this mixed solution 40 DEG C, ultrasonic power performs ultrasonic response 2 hours under being the condition of 280W;
Then, suction filtration process is performed to the suspension obtained through ultrasonic process, and obtain after adopting the process of washed with de-ionized water suction filtration include tin ash-Graphene at interior filter cake, finally by obtained solid freeze drying process 60 hours, obtained basic nano-stannic oxide-graphene composite material product in chondritic thus.
Embodiment 3
Deionized water 80ml is added as solvent in reaction vessel, the sub-tin of dichloro of the graphene oxide and 23.3mg that then successively add 372mg is wherein as solute, then mix and blend 60 minutes, obtains the mixed solution of graphene oxide and tin ash predecessor thus;
Then, by this mixed solution 30 DEG C, ultrasonic power performs ultrasonic response 2 hours under being the condition of 300W;
Then, suction filtration process is performed to the suspension obtained through ultrasonic process, and obtain after adopting the process of washed with de-ionized water suction filtration include tin ash-Graphene at interior filter cake, finally by obtained solid freeze drying process 72 hours, obtained basic nano-stannic oxide-graphene composite material product in chondritic thus.
Embodiment 4
Deionized water 100ml is added as solvent in reaction vessel, the sub-tin of dichloro of the graphene oxide and 10mg that then successively add 57mg is wherein as solute, then mix and blend 60 minutes, obtains the mixed solution of graphene oxide and tin ash predecessor thus;
Then, by this mixed solution 35 DEG C, ultrasonic power performs ultrasonic response 1.5 hours under being the condition of 100W;
Then, suction filtration process is performed to the suspension obtained through ultrasonic process, and obtain after adopting the process of washed with de-ionized water suction filtration include tin ash-Graphene at interior filter cake, finally by obtained solid freeze drying process 72 hours, obtained basic nano-stannic oxide-graphene composite material product in chondritic thus.
Embodiment 5
Deionized water 80ml is added as solvent in reaction vessel, the sub-tin of dichloro of the graphene oxide and 8mg that then successively add 45.7mg is wherein as solute, then mix and blend 60 minutes, obtains the mixed solution of graphene oxide and tin ash predecessor thus;
Then, by this mixed solution 28 DEG C, ultrasonic power performs ultrasonic response 1 hour under being the condition of 150W;
Then, suction filtration process is performed to the suspension obtained through ultrasonic process, and obtain after adopting the process of washed with de-ionized water suction filtration include tin ash-Graphene at interior filter cake, finally by obtained solid freeze drying process 72 hours, obtained basic nano-stannic oxide-graphene composite material product in chondritic thus.
Embodiment 6
Deionized water 100ml is added as solvent in reaction vessel, the sub-tin of dichloro of the graphene oxide and 10mg that then successively add 57.1mg is wherein as solute, then mix and blend 30 minutes, obtains the mixed solution of graphene oxide and tin ash predecessor thus;
Then, by this mixed solution 35 DEG C, ultrasonic power performs ultrasonic response 2 hours under being the condition of 200W;
Then, suction filtration process is performed to the suspension obtained through ultrasonic process, and obtain after adopting the process of washed with de-ionized water suction filtration include tin ash-Graphene at interior filter cake, finally by obtained solid freeze drying process 12 hours, obtained basic nano-stannic oxide-graphene composite material product in chondritic thus.
Below by for the sample obtained by embodiment 1, introduce and the composite products obtained according to the present invention analyzed and the process of Performance Detection.First the nickel foam of sheet can be cut into about 1*2cm
2size, then nickel foam cleaned and activate: nickel foam ethanol is carried out ultrasonic cleaning 10 minutes, then nickel foam deionized water being carried out ultrasonic cleaning 10 minutes.After wash phase completes, nickel foam is proceeded to baking oven and dry 30 minutes under the condition of 100 DEG C, the moisture of removing nickel foam absorption.Obtained nano-stannic oxide-graphene composite material blade is cut small pieces, grinds on alms bowl at agate and mill, to be ground evenly after load sample bottle.Assay balance takes this composite material 1.0mg and on nickel foam after being transferred to previous processed (such as, under the pressure of 20Mpa, composite material can be pressed onto on nickel foam with infrared tablet press machine, the sheet active material difficult drop-off that this pressure is pressed, also not easily breaks nickel foam simultaneously).Then just can adopt conventional three-electrode system, carry out cyclic voltammetry scan and constant current charge-discharge scanning.The nickel foam of composite material load is as work electrode, and the Pt electrode of light is as auxiliary electrode, and calomel electrode is as reference electrode.Electrolyte adopts the KOH solution of 0.1mol/L.For cyclic voltammetry scan, sweep speed is test under the condition of 10mV/s, 20mV/s, 50mV/s, 100mV/s and 200mV/s.For constant current charge-discharge, test under the condition of 1mA/mg and 2mA/mg.
Fig. 2 b is the cyclic voltammetry curve of this material, is to test under the condition of 10mV/s, 20mV/s, 50mV/s, 100mV/s and 200mV/s in sweep speed, its curve close to the invertibity of rectangle illustrative material and capacitive character more excellent.Galvanostatic charge/discharge is one of method of test capacitors capacity, for according to the tin ash-graphene composite material obtained by preparation method of the present invention by the constant current charge-discharge result of Fig. 2 c and 2d in can find out, this composite material single discharge and recharge is that the isosceles triangle of approximate test has reasonable symmetry, voltage linear change in time repeatedly after discharge and recharge curve substantially constant, this illustrates that electrode charge and discharge stable performance good reversibility electrode and electrolyte interface form reasonable charge accumulated and release, the ratio capacitance of electrode material is gone out for being about 212F/g according to discharge curve and formulae discovery.
Fig. 2 a and 2e is transmission electron microscope photo (TEM) according to the nano-stannic oxide obtained by the embodiment of the present invention 1-graphene composite material product and X ray diffracting spectrum (XRD) respectively.As can be seen from 2a figure, in this composite material, the average diameter of particles of nano-stannic oxide is about 5-8nm.And be dispersed in uniformly on graphenic surface.In addition, the XRD test of Fig. 2 e demonstrates prepared composite material thing in 2 θ=34.6 ° (101), there is the characteristic diffraction peak of the tin ash different crystal forms of the correspondence of standard in 38.5 ° (200) and 52.1 ° of (211) places, the characteristic diffraction peak of Graphene has appearred in these external 2 θ=26.6 °.Integral composite presents excellent performance index.Such as, when it is as super capacitor material time, its ratio capacitance is greater than traditional pure material with carbon element; When it is as lithium ion battery negative, possess the advantages such as charge/discharge capacity is high, cycle performance; This composite material also can be used as the electrode, field-effect transistor etc. of fuel cell, therefore possesses the potentiality of replacing traditional devices material and application prospect widely.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (1)
1. for the preparation of a method for nano-stannic oxide-graphene composite material, it is characterized in that, the method comprises the following steps:
A () take deionized water as solvent, successively add as the graphene oxide of solute and the sub-tin of dichloro and perform mix and blend, wherein charge ratio controls as in 80ml deionized water, the mass ratio of graphene oxide and the sub-tin of dichloro is 106.7mg:18.7mg, then mix and blend about 1 minute, performs oxidation-reduction reaction thus and obtains the mixed solution comprising graphene oxide-tin ash presoma; And in this course of reaction, do not add any organic solvent;
B obtained mixed solution is performed ultrasonic reaction 1.5 hours at 25 DEG C of temperature, ultrasonic power under being the condition of 120W by ();
C () performs suction filtration process to the suspension obtained through above-mentioned ultrasonic process, obtain thus including tin ash-graphene complex at interior filter cake, then adopts the filter cake after the process of washed with de-ionized water suction filtration;
D () is finally by the solid freeze drying process 12 hours of gained, namely nano-stannic oxide-graphene composite material the product in chondritic is directly obtained, in this composite material, the average diameter of nano-stannic oxide particle is 5nm to 8nm, and is dispersed on the surface of Graphene; In addition, when it is as electrode material, possess charge-discharge performance and stablize the characteristic with good reversibility, and ratio capacitance is 212F/g.
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| CN103326007B (en) * | 2013-06-25 | 2015-12-09 | 上海交通大学 | The preparation method of three-dimensional graphite thiazolinyl tin dioxide composite material and application thereof |
| CN103995088B (en) * | 2014-05-26 | 2015-12-02 | 太原理工大学 | The preparation method of Graphene/tin oxide nano composite material and application thereof |
| CN104198553B (en) * | 2014-09-25 | 2017-05-31 | 普旭力 | A kind of biological sensor sensing film and preparation method thereof and purposes |
| CN105006560A (en) * | 2014-12-19 | 2015-10-28 | 上海杉杉科技有限公司 | Nano-SnO2 graphene composite material for lithium ion battery and preparation method thereof |
| CN104900859B (en) * | 2015-06-01 | 2017-08-11 | 合肥工业大学 | A kind of porous SnO2Nanosphere/graphene composite material and preparation method thereof |
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| CN105839078B (en) * | 2016-04-13 | 2018-04-27 | 西安近代化学研究所 | A kind of method that graphene nano Composite Energetic Materials are prepared using technique for atomic layer deposition |
| CN107658148A (en) * | 2016-07-25 | 2018-02-02 | 天津大学 | A kind of method for preparing graphene tin dioxide composite material and its application in terms of energy storage |
| CN107124778B (en) * | 2017-05-03 | 2022-07-05 | 广州厨霸电器有限公司 | Far infrared electrothermal film, process for manufacturing far infrared electrothermal film and electric heater |
| CN106990142A (en) * | 2017-05-09 | 2017-07-28 | 大连理工大学 | A kind of NO based on graphene/tin dioxide quantal-point composite2Sensor and preparation method thereof |
| CN112363460A (en) * | 2019-12-19 | 2021-02-12 | 广州见正健康科技股份有限公司 | Process for manufacturing far infrared electrothermal film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927979A (en) * | 2010-08-03 | 2010-12-29 | 复旦大学 | Stannic oxide/ graphene nano composite as well as preparation method and application thereof |
-
2012
- 2012-11-28 CN CN201210494621.0A patent/CN103035916B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927979A (en) * | 2010-08-03 | 2010-12-29 | 复旦大学 | Stannic oxide/ graphene nano composite as well as preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Bivalent tin ion assisted reduction for preparing graphene/SnO2 composite with good cyclic performance and lithium storage capacity;Bing Zhao, et al.;《Electrochimica Acta》;20110621;第56卷;第7340页摘要，第7341页第2节实验，第7342页，图2-3 * |
| Nanocrystal-SnO2-loaded Graphene with Improved Li-Storage Properities Prepared by a Facile One-Pot Hydrothermal Route;Jian Xie, et al.;《Int.J.Electrochem.Sci.》;20111101;第6卷;全文 * |
| Preparation of SnO2-Nanocrystal/Graphene-Nanosheets Composites and Their Lithium Storage Ability;Yueming Li, et al.;《J.Phys.Chem.C》;20101111;第114卷(第49期);第2.1节实验 * |
| 石墨烯担载SnO2纳米复合材料的电化学性能研究;龚文照等;《化工新型材料》;20120731;第40卷(第7期);全文 * |
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