CN103094539B - Preparation method of tin dioxide quantum dot graphene sheet composite - Google Patents
Preparation method of tin dioxide quantum dot graphene sheet composite Download PDFInfo
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- CN103094539B CN103094539B CN201210491147.6A CN201210491147A CN103094539B CN 103094539 B CN103094539 B CN 103094539B CN 201210491147 A CN201210491147 A CN 201210491147A CN 103094539 B CN103094539 B CN 103094539B
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of a tin dioxide quantum dot graphene sheet composite. The process comprises the following steps: a) preparing graphene oxide; and b) and dispersing a prepared GO (graphene oxide) solution in deionized water, performing ultrasonic treatment to fully disperse GO in water, slowly dripping an SnCl2 solution while stirring and then performing ultrasonic treatment, further performing centrifugal washing on a product, drying in a vacuum drying box, and finally annealing a sample in an N2 atmosphere at the temperature of 600 DEG C to prepare the tin dioxide quantum dot (4-6nm) graphene composite. According to the preparation method disclosed by the invention, tin dioxide can be uniformly distributed on the two sides of graphene by controlling the concentration of the graphene solution and the SnCl2 solution, the stirring time, the ultrasonic treatment time and the annealing temperature. With the rapid development and the wide application of lithium batteries, the preparation method disclosed by the invention has great application prospects in the field of electrochemistry.
Description
Technical field
The preparation method of a kind of tin dioxide quantal-point graphene film compound involved in the present invention, belongs to metal oxide graphene complex preparation technology and technical field of electrochemistry.
Background technology
Lithium ion battery has the advantages that high density, height ratio capacity and quality are little, has obtained application very widely in mobile phone, notebook computer and various instrument.Tin ash has the plurality of advantages such as height ratio capacity (783mAh/g), price be low as a kind of oxide of rutile structure, has obtained increasing concern in the application of lithium ion battery negative material.Yet, because tin ash can make battery capacity sharply reduce along with lithium ion embeds the change in volume that embedding goes out to produce in the process of charge/discharge, limited to a great extent the application of tin ash in cell negative electrode material.In order to address this problem, research is at present compound by tin ash and Graphene, has improved to a certain extent the chemical property of tin ash.Graphene is a kind of material with carbon element of two dimension, has good conductivity and chemical stability, high specific area.Graphene, as the carrier of stannic oxide particle, has not only improved the reversible specific capacity of material, has also improved cycle performance.At present, the method for preparing metal oxide graphene complex is a lot, and some complex methods are too loaded down with trivial details, the extremely difficult pattern of controlling material of some synthetic methods.The present invention adopts ultrasonic method, the solution concentration of reacting by control and stirring, ultrasonic time, and annealing temperature, prepares tin ash graphene composite material.Test result shows: the diameter of stannic oxide particle is distributed between 4 to 6nm, is evenly distributed on the both sides of graphene film, has good using value.
Summary of the invention
The defect existing for prior art, the object of this invention is to provide a kind of preparation method of tin dioxide quantal-point graphene film compound, is the preparation method of the good tin ash graphene complex of a kind of simple, repeatability and operability.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for tin dioxide quantal-point graphene film compound, has following steps:
A. the preparation of graphene oxide: the potassium peroxydisulfate that is 1:1 by mass ratio and phosphorus pentoxide, be dissolved in the appropriate concentrated sulfuric acid, be heated to 80
oc; Then 3 ~ 5g native graphite is added to above-mentioned solution, constant temperature 4h; Be cooled to room temperature, after the deionized water dilution with 300 ~ 400ml, standing over night; Washing, suction filtration; 60
odry in C vacuum drying chamber; The precursor obtaining is joined in the ice bath concentrated sulfuric acid of 120ml, under agitation slowly add the KMnO of 0.09 ~ 0.11mol
4, in the process adding, maintain the temperature at 0 ~ 5
oc; Then temperature is controlled to 35
oc is stirred to abundant reaction; Add the dilution of 250 ~ 300ml ionized water, in dilution, also will in ice bath, make temperature lower than 50
oc; After stirring, add enough deionized waters, and add at once the H of 20ml 30%
2o
2, mixture produces bubble, and color becomes glassy yellow; By said mixture suction filtration, and with the watery hydrochloric acid washing of the 1:10 of 1L, filter and remove part metals ion; Use again deionized water washing and filtering, remove unnecessary acid; Above-mentioned solution is dissolved in the water, and then the ultrasonic Solution Dispersion that makes is even, obtains graphene oxide solution, and after centrifugation, the product that obtains brownish black at air drying is graphene oxide;
B. the graphene oxide solution of volume ratio 2:1 and deionized water are mixed, the ultrasonic graphene oxide that makes is well-dispersed in water, slowly drips 10ml SnCl in vigorous stirring
2solution, fully stirs, then ultrasonic; By the product centrifuge washing obtaining, fully dry in vacuum drying chamber, finally by sample at N
2high annealing in atmosphere, temperature is 600
oc, makes tin dioxide quantal-point graphene complex.
Compared with prior art, the present invention has following outstanding feature and significant progressive:
The tin dioxide quantal-point size a process for preparing, 4 to 6nm, is dispersed in the both sides of graphene film.In the process forming at compound, Graphene sheet structure has hindered the reunion of tin ash, meanwhile, the tin dioxide quantal-point being attached to above graphene film has also been avoided the accumulation of graphene film effectively, has played very crucial effect in preparing the process of graphene film.Along with develop rapidly and the extensive use of lithium battery, the present invention has good application prospect in electrochemical field.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of Graphene (a), tin ash graphene complex (b), tin ash (c).
Fig. 2 is the scanning electron microscope (SEM) photograph of Graphene (a), tin ash graphene complex (b).
Fig. 3 is the transmission electron microscope picture that the present invention prepares the tin ash graphene composite material of gained.
Fig. 4 is the Raman spectrum of Graphene (a), tin ash graphene complex (b).
Fig. 5 is the thermogravimetric collection of illustrative plates of Graphene (a), tin ash graphene complex (b).
Fig. 6 is the formation mechanism figure of the present invention's tin ash graphene composite material of preparing gained.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is done to further statement.
A preparation method for tin dioxide quantal-point graphene film compound, has following steps:
A. the preparation of graphene oxide: by potassium peroxydisulfate (K
2s
2o
8) 2.5g, phosphorus pentoxide (P
2o
5) 2.5g, be dissolved in the 20ml concentrated sulfuric acid, be heated to 80
0c; Then 3g native graphite is added to above-mentioned solution, constant temperature 4.5h; Be cooled to room temperature, with after the dilution of 350ml deionized water, standing over night; Washing, suction filtration; 60
0dry in C vacuum drying chamber; The pre-oxidation thing obtaining is joined in the concentrated sulfuric acid of ice bath of 120ml, under agitation slowly join 15g KMnO
4, in the process adding, maintain the temperature at 5
obelow C.Then be that temperature is controlled at 35
oc stirs 2h.Add the dilution of 250ml deionized water, in dilution, also will in ice bath, make temperature lower than 50
oc.Stir again 2h, then add 0.7L deionized water, and add at once the H of 20ml 30%
2o
2, mixture produces bubble, and color has become glassy yellow, reaction terminating after about 0.5h.By said mixture suction filtration, and with the watery hydrochloric acid washing of the 1:10 of 1L, filter one and remove part metals ion; With 1L water washing, filter again, to remove unnecessary acid; Above-mentioned solution is dissolved in 1L water, and then ultrasonic 0.5h left and right under 100W ultrasonic power, obtains graphene oxide solution (GO), and after centrifugation, the product that obtains brownish black at air drying is the graphene oxide needing.
B. by the GO Solution Dispersion of 100ml in 50ml deionized water, ultrasonic 30min, is well-dispersed in water GO, slowly drips 10ml SnCl in vigorous stirring
2(0.45g) solution, stirs 30min, then ultrasonic 60min under 100W ultrasonic power.By the product centrifuge washing obtaining 3 times, 60
ofully dry in the vacuum drying chamber of C, finally by sample 600
oat the temperature of C at N
2the 3h that anneals in atmosphere, makes tin dioxide quantal-point graphene complex.The tin dioxide quantal-point size of preparing under above-mentioned experiment condition, 4 to 6nm, is dispersed in the both sides of graphene film uniformly.
As shown in Figure 1, be the X-ray diffractogram of Graphene (a), tin ash graphene complex (b), tin ash (c)
,x-ray diffraction (XRD) research shows: the main indices of crystallographic plane of compound and the standard X-ray diffraction of Tetragonal tin ash (PDF document number: 77-0447) basically identical, for example: Tetragonal tin ash (110), (101), (200), (211), and (002) face (220), there is no other impurity peaks or other tin oxide peak, illustrate that the sample preparing comprises Tetragonal stannic oxide particle.After stannic oxide particle and Graphene are compound, the diffraction maximum of Graphene disappears.Presentation of results: graphene film contributes to form tin dioxide quantal-point, and the tin dioxide quantal-point adhering in Graphene both sides has also been avoided the accumulation of annealing stage Graphene.
As shown in Figure 2, be the scanning electron microscope (SEM) photograph of Graphene (a), tin ash graphene complex (b).From figure (a), can find out and successfully prepare graphene film.In figure (b), can clearly observe tin dioxide quantal-point is evenly distributed on above graphene film.Result shows: the compound that has successfully made tin dioxide quantal-point Graphene.
As shown in Figure 3, the transmission electron microscope picture of preparing the tin ash graphene composite material of gained for the present invention.High-resolution-ration transmission electric-lens test shows: tin dioxide quantal-point is evenly distributed in above graphene film, and lateral size of dots is between 4 to 6 nanometers.Tin dioxide quantal-point crystallization is perfect, spacing of lattice approximately 0.33 nanometer, corresponding (110) crystal face.Electron energy loss spectroscopy (EELS) test shows: in compound, comprise tin, oxygen and carbon, proved that product is exactly tin ash graphene complex.
As shown in Figure 4, be the Raman spectrum of Graphene (a), tin ash graphene complex (b).Raman spectrum mainly comprises D peak (~ 1335 cm
-1) and G peak (~ 1593 cm
-1).D peak and G peak are all the characteristic peaks of carbon, and wherein D peak has reflected the defect of material with carbon element, border structure and crystallization degree, and G peak is decided by electron conjugated degree.
i d / I g the variation of ratio has reflected the microstructure change of material with carbon element, and the peak that calculates compound is by force that 1.20 peaks with respect to Graphene strong (1.09) increase to some extent.Result shows: the accumulation of tin dioxide quantal-point has obvious impact to the structure of Graphene.
As shown in Figure 5, be the thermogravimetric collection of illustrative plates of Graphene (a), tin ash graphene complex (b).Thermogravimetric test shows: the thermal loss of Graphene is 16.65%, and the thermal loss of compound is 26.27%.(Fig. 5).The reason that the loss of compound thermogravimetric increases is to some extent crystallization evaporation of water in tin ash.
As shown in Figure 6, the formation mechanism figure for preparing the tin ash graphene composite material of gained for the present invention.It is as follows that tin dioxide quantal-point graphene complex forms mechanism: graphene oxide includes a large amount of hydroxyls and carboxyl, electronegative.After tin ion adds, stir and ultrasonic effect under, the electronegative functional group of tin ion and Graphene combines closely, and is oxidized in the process of tetravalence state the reduction of simultaneous carbon at tin ion.The complex compound of the hydroxy combining formation tin in tetravalent tin ion and solution is attached to the surface of Graphene.At annealing stage, be that the remaining functional group in graphene oxide surface can be converted into water, carbon dioxide and carbon monoxide and forms Graphene, the hydroxo complex of the tin formation tin ash that dries out simultaneously.
Claims (1)
1. a preparation method for tin dioxide quantal-point graphene film compound, is characterized in that, has following steps:
A. the preparation of graphene oxide: the potassium peroxydisulfate that is 1:1 by mass ratio and phosphorus pentoxide, be dissolved in the appropriate concentrated sulfuric acid, be heated to 80
oc; Then 3 ~ 5g native graphite is added to above-mentioned solution, constant temperature 4.5h; Be cooled to room temperature, after the deionized water dilution with 300 ~ 400ml, standing over night; Washing, suction filtration; 60
odry in C vacuum drying chamber; The pre-oxidation thing obtaining is joined in the ice bath concentrated sulfuric acid of 120ml, under agitation slowly add the KMnO of 0.09 ~ 0.11mol
4, in the process adding, maintain the temperature at 0 ~ 5
oc; Then temperature is controlled to 35
oc is stirred to abundant reaction; Add the dilution of 250 ~ 300ml deionized water, in dilution, also will in ice bath, make temperature lower than 50
oc; After stirring, add enough deionized waters, and add at once the H of 20ml 30%
2o
2, mixture produces bubble, and color becomes glassy yellow; By said mixture suction filtration, and with the watery hydrochloric acid washing of the 1:10 of 1L, filter and remove part metals ion; Use again deionized water washing and filtering, remove unnecessary acid; Above-mentioned solution is dissolved in the water, and then the ultrasonic Solution Dispersion that makes is even, obtains graphene oxide solution, and after centrifugation, the product that obtains brownish black at air drying is graphene oxide;
B. the graphene oxide solution of volume ratio 2:1 and deionized water are mixed, the ultrasonic graphene oxide that makes is well-dispersed in water, slowly drips 0.45 gram of SnCl in vigorous stirring
2, fully stir, then ultrasonic; By the product centrifuge washing obtaining, fully dry in vacuum drying chamber, finally by sample at N
2high annealing in atmosphere, temperature is 600
oc, makes tin dioxide quantal-point graphene complex.
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| CN103094539B true CN103094539B (en) | 2014-12-03 |
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| CN103482618B (en) * | 2013-09-09 | 2015-12-02 | 东南大学 | A kind of preparation method of graphene-tin dioxide nanoparticle composite material |
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| 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 |
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| KR101117689B1 (en) * | 2005-01-22 | 2012-02-29 | 삼성전자주식회사 | Photoreceptive layer comprising various dye and solar cells using the same |
| JP2007115699A (en) * | 2005-10-21 | 2007-05-10 | Samsung Electronics Co Ltd | Semiconductor electrode, its manufacturing method and solar cell including the same |
| US8119288B2 (en) * | 2007-11-05 | 2012-02-21 | Nanotek Instruments, Inc. | Hybrid anode compositions for lithium ion batteries |
| US7745047B2 (en) * | 2007-11-05 | 2010-06-29 | Nanotek Instruments, Inc. | Nano graphene platelet-base composite anode compositions for lithium ion batteries |
| CN101428847B (en) * | 2008-12-15 | 2010-06-02 | 吉林大学 | Process for producing nanostructured tin dioxide lithium ion battery negative pole material |
| CN101478043A (en) * | 2009-01-08 | 2009-07-08 | 上海交通大学 | Negative pole material for lithium ionic cell and preparation process thereof |
| JP2011091032A (en) * | 2009-09-25 | 2011-05-06 | Nippon Shokubai Co Ltd | Manufacturing method of electrode for quantum dot sensitized solar cell, electrode for quantum dot sensitized solar cell, and quantum dot sensitized solar cell |
| CN101823760B (en) * | 2010-05-13 | 2012-09-05 | 西安交通大学 | Method for preparing nanometer foam stannic oxide of lithium ion battery cathode material |
| CN101894678B (en) * | 2010-06-07 | 2012-06-06 | 天津大学 | Spongy quantum dot solar cell and preparation method thereof |
| CN101969113B (en) * | 2010-09-21 | 2012-11-07 | 上海大学 | Preparation method of graphene-base tin dioxide composite anode material for lithium ion batteries |
| CN102176382B (en) * | 2011-01-31 | 2013-10-16 | 中国科学院上海硅酸盐研究所 | Method for preparing grapheme-quantum dot composite film and solar battery structured by using same |
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