CN104176728B - A kind of preparation method who controls stannic oxide/graphene nano structure and morphology - Google Patents
A kind of preparation method who controls stannic oxide/graphene nano structure and morphology Download PDFInfo
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- CN104176728B CN104176728B CN201410145171.3A CN201410145171A CN104176728B CN 104176728 B CN104176728 B CN 104176728B CN 201410145171 A CN201410145171 A CN 201410145171A CN 104176728 B CN104176728 B CN 104176728B
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Abstract
The invention discloses a kind of preparation method who controls stannic oxide/graphene nano structure and morphology. By the ultrasonic graphite oxide powder suspension that obtains 0.5-2.0mg/mL in deionized water that is distributed to; Add 10-30mg polyvinyl alcohol and NiCl2, use respectively ultrasonic and magnetic agitation each 1 hour; Then at 120-200 DEG C of a certain isothermal reaction 10-16h; Product is through washing, more than freeze drying 5h. The method is by introducing different amount Ni2+With change temperature, control stannic oxide/graphene nano sheet self assembly behavior, the main pattern of product comprises individual layer, multilayer and tridimensional network. This technology has overcome the unmanageable difficult problem of two-dimensional sheet nano material self assembly behavior, has obtained and has had high capacity and the stable super capacitor material of charge-discharge performance. Compared with conventional method, install simple, easy to operate, productive rate is high and controllability good, for nano material self assembly, performance optimization and device significant.
Description
Technical field
The present invention relates to a kind of preparation method who controls stannic oxide/graphene nano structure and morphology, especially, for energy storage materialThe preparation method of the different-shape stannic oxide/graphene nano structure of material. Adopt hydro-thermal method, by introduce Ni in reaction solution2+FromSon also regulates Ni2+Concentration and reaction temperature realize the pattern control of nanostructured, and pattern mainly comprises individual layer, multilayer and three dimensional networkShape.
Background technology
Graphene is by monolayer honeycomb shape hexagon sp2The monatomic bed thickness two-dimensional material that hydridization carbon atom forms, hasExcellent electricity, heat conductivity and mechanical performance. As a branch of Graphene, material normally for graphene oxide (being called for short GO)Utilize strong oxidizer that natural graphite oxide powder oxidation is made, the covalency oxygen-containing functional group that surface is abundant and defect make it have to be permittedMany potential application advantages. For example, high density energy storage material; C catalyst efficient and with low cost; As high-efficient oxidantBe widely used in organic reaction system, comprise that olefin oxidation becomes polyester, methylenedioxy phenoxy changes into acetaldehyde and diarylmethanes is oxidized toKetone etc.; In addition, the existence of polarity oxygen-containing functional group makes GO have very strong hydrophily, causes it at multi-solvents (especially water)In show good dispersiveness, this is extremely important for commercial Application; These functional groups contribute to its finishing or functionChange. At present, GO nanostructured has been successfully applied to many necks such as microelectromechanical systems, biology sensor and organizational projectTerritory.
As energy storage material, the charge-discharge performance of GO is also subject to the impact of nanostructure size and pattern. Realize GO nanometerThe pattern control of structure has very important significance to its performance regulation and control and optimization. But the research work of this respect is still freshThere is report. Develop a kind of simple, economy and the large preparation method of the scope of application, have important for obtaining excellent capacitive propertyMeaning. The invention discloses one step hydro thermal method technology path, by introducing the Ni of different amounts2+Ion and change reaction temperature,Reach the object of controlling GO nanometer sheet self assembly behavior, thereby realize the pattern regulation and control of GO nanostructured, product comprises individual layer, manyLayer and tridimensional network. The method device is simple, easily operation, controllability are good, has very strong applicability.
Summary of the invention
Object of the present invention: provide a kind of preparation method who controls stannic oxide/graphene nano structure and morphology, main pattern bagDraw together individual layer, multilayer and tridimensional network. The method is by introducing different amount Ni2+With change reaction temperature, reach and control GOThe object of nanometer sheet self assembly behavior. This technology has overcome the unmanageable difficult problem of flake nano material self assembly behavior, therebyRealized and in a reaction system, prepared multiple different-shape stannic oxide/graphene nano structure, obtained have high capacity andThe super capacitor material that charge-discharge performance is stable; For controlled self assembly, performance optimization and the device thereof of nano material provide onePlant new approach.
Technical scheme of the present invention: obtain graphite oxide as raw material adopts Hummer legal system taking the graphite powder of buying on marketPowder; Get 20-40mg graphite oxide powder and join in deionized water, and ultrasonic dispersion obtains the suspension that concentration is 0.5-2.0mg/mLLiquid; Continuing, under ultrasonication, to add the NiCl of 10-30mg polyvinyl alcohol (PVA) and certain mass2·6H2O, mixed solution dividesDo not use ultrasonic and magnetic agitation each 1 hour; Then mixed solution is transferred in the polytetrafluoroethylliner liner of reactor, at 120-Under a certain constant temperature within the scope of 200 DEG C, react 10-16h; Reaction finish after, naturally cool to room temperature, product through repeatedly centrifugal, washWash, finally in freeze drier more than dry 5h.
1. as optimal selection, the reaction temperature of preparing individual layer, multilayer stannic oxide/graphene nano structure is 120-150 DEG C,The reaction temperature of preparing three-dimensional netted nanostructured is 160-200 DEG C.
If when 2. hydrothermal temperature is lower than 120 DEG C, there is the aggregation of graphene oxide in product.
3. in order to ensure that suspension mixes, need to be respectively by each 1 hour of ultrasonic and magnetic agitation.
4. as optimal selection, Ni2+With the scope of graphite oxide powder mol ratio (r) be: do not add Ni2+Time, product is threeDimension network structure; R=0.02～0.10 o'clock, individual layer nanometer sheet; R=0.10～0.15 o'clock, multiple-layer overlapped nanostructured.
⑤Ni2+The amount that ion adds can not be too much, in the time of r > 0.15, can generate β-Ni (OH)2Impurity.
6. as optimal selection, the concentration of graphite oxide powder suspension is 0.5-2.0mg/mL, and PVA addition is 10-30mg。
7. the hydro-thermal reaction time of different-shape stannic oxide/graphene nano structure is 10-16h; Product through repeatedly centrifugal,Washing, finally in freeze drier more than dry 5h.
Hydro-thermal method has overcome the unmanageable difficult problem of flake nano material self assembly behavior, has realized a reaction systemThe multiple different-shape stannic oxide/graphene nano of middle preparation structure; GO product has high heat endurance and chemical stability, performanceCan in a big way, regulate and control, therefore have potential in many fields such as micro-nano electronic mechanical system, energy storage and bio-sensingsApplication prospect.
Beneficial effect of the present invention:
In conjunction with the advantage of hydro-thermal method reaction, by introducing Ni2+Ion and adjusting reaction temperature realize stannic oxide/graphene nanoThe pattern control of structure. Ni2+The concentration of ion plays an important role to the pattern control of product. The method is easy to operate, productPrepared by purity scale higher and easily separated, that easily realize material. The optimization of pattern control such as capacitive property provides guarantorBarrier.
The preparation method that the present invention proposes has the following advantages:
(1) product has high heat endurance and chemical stability;
(2) controllability is good. Only regulate Ni2+Concentration and hydrothermal temperature, realize the pattern of stannic oxide/graphene nano structureControl.
(3) productive rate of product is high.
(4) performance is controlled. Because the performance height of GO nanostructured depends on pattern, thereby can in a big way, adjustControl.
(5) preparation method is simple, with low cost, has certain industrial applications prospect.
Brief description of the drawings:
Fig. 1 is the SEM figure of different-shape stannic oxide/graphene nano structure. (a-b) three-dimensional netted, (c) r=0.025, individual layerGraphene oxide; (d) r=0.050, part mono-layer graphite oxide alkene; (e) r=0.100, individual layer, multilayer graphene oxide mixedCompound; (f) r=0.150, multilayer graphene oxide.
Fig. 2 is (a-b) three-dimensional netted and (c-d) TEM picture of multi-layer nano structure graphene oxide material.
Fig. 3 is different temperatures, different Ni2+XRD collection of illustrative plates with product under graphite oxide powder mol ratio (r) condition.
Fig. 4 is the CV figure of different-shape stannic oxide/graphene nano structural modification electrode, sweep speed 50mVs-1。
The quality of the lower stannic oxide/graphene nano structural modification electrode of the different charge/discharge rate of Fig. 5 (v) compares capacitance variations.
Detailed description of the invention
The preparation method who controls stannic oxide/graphene nano structure and morphology in the present invention, detailed description of the invention is as follows:
Embodiment 1
Three-dimensional netted GO nanostructured: utilize improved Hummer method, make taking the graphite powder bought on market as raw materialGraphite oxide powder; Get 30.2mg graphite oxide powder and join in deionized water, and ultrasonic dispersion to obtain concentration be 1.0mg/mL'sSuspension; Continuing under ultrasonication, to add 20mg polyvinyl alcohol, mixed solution is used respectively ultrasonic and magnetic agitation each 1 hour;Then mixed solution is transferred in the polytetrafluoroethylliner liner of reactor, at 180 DEG C, reacted 12h; After reaction finishes, natureBe cooled to room temperature, product, through centrifugal, washing repeatedly, is finally dried 20h in freeze drier.
Fig. 1 a-b is the representative SEM figure of the product that obtains of embodiment 1. Can see, product has obvious three dimensional networkShape structure, is to be interwoven in three dimensions by very thin nanometer sheet, forms a lot of holes. Because polyvinyl alcohol can infiltrateIn the hole of three-dimensional netted graphene oxide, this nano structural material has good pliability, in aggressive bend and torsionSituation under can not rupture.
Embodiment 2
Reaction temperature is 120 DEG C, and other condition is with example 1.
Embodiment 2 products are the aggregation that pattern is irregular and size is very large. This is due at lower temperature, π-πThe attraction that interaction produces, much larger than the repulsive force of random alignment, has caused the tightly packed formation of stannic oxide/graphene nano sheetProduct form. This shows, temperature is during lower than 120 DEG C, and the three-dimensional netted nanostructured of graphene oxide cannot obtain.
Embodiment 3
Ni2+With graphite oxide powder mol ratio (r) be 0.025 o'clock, reaction temperature is 120 DEG C, other condition is with embodiment 1.
Embodiment 4
Ni2+During with the mol ratio r=0.05 of presoma, other condition is with embodiment 3.
Embodiment 5
Ni2+During with the mol ratio r=0.10 of presoma, other condition is with embodiment 3.
Embodiment 6
Ni2+During with the mol ratio r=0.15 of presoma, other condition is with embodiment 3.
Fig. 1 (c-f) is for obtaining the SEM picture of product under different r conditions. Can see, along with the increase of r, graphite oxideThere is the obvious alternation from individual layer to multilayer in the pattern of alkene nanostructured. In the time of r=0.025 (embodiment 3), product is evident as(Fig. 1 c) for individual layer nanometer sheet; In the time of r=0.05 (embodiment 4), portion of product is mono-layer graphite oxide alkene, but still is individual layer nanometerSheet is that (Fig. 1 d) for master; In the time of r=0.1 (embodiment 5), product is the mixture of individual layer and multilayer stannic oxide/graphene nano structure(Fig. 1 e); In the time that r is increased to 0.15 (embodiment 6), product is all that (Fig. 1 f) for multilayer stannic oxide/graphene nano structure.
Fig. 2 a is the TEM picture of the three-dimensional netted nanostructured that obtains of embodiment 1. Due to high-temperature water thermal response, paper foldThe nanostructured of shape generates. (Fig. 2 b) shows the TEM picture amplifying, and three-dimensional netted nanostructured has interconnected bending knotStructure, and edge rough. Illustration is the amplification TEM figure at edge, has confirmed that it is made up of stannic oxide/graphene nano sheet. FromFig. 2 c-d can find out, product has transparent layer structure, and some folds appear at relatively coarse surface. Depositing of these foldsReduce surperficial energy, be conducive to the stability of sandwich construction. Lip-deep fold has the height of 5-10nm. As 2d illustration instituteShow, carbon lattice fringe is easy to appear at fold place, and interplanar distance is 0.38nm.
Fig. 3 is different temperatures, different Ni2+XRD collection of illustrative plates with product under graphite oxide powder mol ratio (r) condition. Can seeArrive, they have similar XRD diffracting spectrum, and 25 ° of broad peaks of locating have confirmed that graphitization characteristic still keeps, this diffraction maximum strongDegree is along with the increase of r reduces gradually. In the time of r=0.15 (embodiment 6), occur corresponding to β-Ni (OH)2(100), (101)(102) diffractive features peak. This result shows, in the time of the stannic oxide/graphene nano structure of preparation multilayer, and the Ni of introducing2+IonConcentration can not be too high, Ni2+Ion does not change component and the microstructure of product, just only the pattern of product is had to impact.
As shown in Figure 4, there is the highest quality by the electrode of three-dimensional netted stannic oxide/graphene nano structural modification and compare electric capacity(91.8Fg-1), the electrode that corresponding individual layer, multilayer graphene oxide are modified, its quality is respectively 59.6Fg than the value of electric capacity-1And 45.4Fg-1. Because quality is directly proportional to the specific area of capacitance material than capacitance, therefore stannic oxide/graphene nano structureQuality declines successively than capacitance should be owing to specific area. The number of plies (LN) of graphene oxide can pass through LN=2620 ×Wt.%C/ specific area is calculated, wherein 2620 (m2g-1) be the theoretical specific area of mono-layer graphite oxide alkene, due to oxygenThere is oxygen atom in functionalized graphene, LN can revise by carbon atom weight ratio (wt.%C), and specific area is with the increasing of the number of pliesAdd and reduce, multilayer stannic oxide/graphene nano structure has minimum specific area.
Fig. 5 has provided three electrodes that individual layer, multilayer and three-dimensional netted graphene oxide are modified, quality than capacitance withThe variation tendency of charge/discharge rate (v). The quality of three electrodes than electric capacity at v=5Vs-1Time be 352Fg-1, and at v=80Vs-1Time be 78Fg-1. But, when v is from 5Vs-1Be increased to 80Vs-1Time three electrodes electric capacity all decline. Wherein, three-dimensionalNetwork structure graphene oxide electrode has kept the highest quality than electric capacity in identical scope, and this may be because three-dimensional is manyThe electric charge that pore structure has been accelerated in charge/discharge process shifts. In addition, compared with individual layer, multilayer graphene oxide electrode, three dimensional networkShape graphene oxide electrode has higher initial mass than electric capacity, and this is because it has higher specific area, and multilayerThe closs packing single layer structure existing in graphene oxide has hindered effective charge transfer process. Particularly, three-dimensional netted nanometerThe quality that structure graphene oxide electrode shows is better than the peak (v=5Vs of report recently than capacitance-1Time, 220Fg-1)。
Claims (6)
1. a preparation method who controls stannic oxide/graphene nano structure and morphology, is characterized in that, adopts hydro-thermal method, by insteadAnswer and in solution, introduce Ni2+Ion also regulates Ni2+With graphite oxide powder mole when hydrothermal temperature realize graphene oxide and receiveThe pattern control of rice structure, pattern comprises individual layer, multilayer and three-dimensional netted; Concrete steps are: with the graphite powder of buying on marketFor adopting Hummer legal system, raw material obtains graphite oxide powder; Get 20-40mg graphite oxide powder and join in deionized water, and ultrasonic pointFall apart and obtain the suspension that concentration is 0.5-2.0mg/mL; Continuing under ultrasonication, add 10-30mg polyvinyl alcohol (PVA) andThe NiCl of certain mass2·6H2O, mixed solution is used respectively ultrasonic and magnetic agitation each 1 hour; Then mixed solution is transferred toIn the polytetrafluoroethylliner liner of reactor, under a certain constant temperature within the scope of 120-200 DEG C, react 10-16h; After reaction finishes,Naturally cool to room temperature, product is through centrifugal, washing repeatedly, finally in freeze drier more than dry 5h.
2. a kind of preparation method who controls stannic oxide/graphene nano structure and morphology according to claim 1, is characterized in that,In order to ensure that suspension mixes, add mixed solution after PVA need to be respectively by each 1 hour of ultrasonic and magnetic agitation.
3. a kind of preparation method who controls stannic oxide/graphene nano structure and morphology according to claim 1, is characterized in that,The concentration of graphite oxide powder suspension is 0.5-2.0mg/mL, and PVA addition is 10-30mg.
4. a kind of preparation method who controls stannic oxide/graphene nano structure and morphology according to claim 1, is characterized in that,Ni2+With the optimum range of graphite oxide powder mol ratio be: when r=0, product is three-dimensional porous netted graphene oxide; R=0.02～0.10, mono-layer graphite oxide alkene; R=0.10～0.15, multilayer stannic oxide/graphene nano structure; Ni2+The amount that ion adds is notCan too much, in the time of r > 0.15, can generate β-Ni (OH)2Impurity.
5. a kind of preparation method who controls stannic oxide/graphene nano structure and morphology according to claim 1, is characterized in that,The optimal reaction temperature of individual layer, multilayer stannic oxide/graphene nano structure is 120-150 DEG C, and three-dimensional netted nanostructured is best anti-Answering temperature is 160-200 DEG C.
6. a kind of preparation method who controls stannic oxide/graphene nano structure and morphology according to claim 1, is characterized in that,The hydro-thermal reaction time of different-shape stannic oxide/graphene nano structure is 10-16h; Product, through centrifugal, washing repeatedly, finally existsIn freeze drier more than dry 5h.
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| CN101993056A (en) * | 2010-12-01 | 2011-03-30 | 天津大学 | Graphene-based porous macroscopic carbon material and preparation method thereof |
| CN102992308A (en) * | 2012-11-21 | 2013-03-27 | 复旦大学 | Graphene with high specific capacitance and preparation method thereof |
| CN103145125A (en) * | 2013-04-01 | 2013-06-12 | 兰州大学 | Preparation method for high adsorptivity three-dimensional self-assembly graphene |
| CN103253655A (en) * | 2013-04-15 | 2013-08-21 | 中国科学院宁波材料技术与工程研究所 | Compound graphene with scattering scale and preparation method thereof |
| CN103545121A (en) * | 2013-10-23 | 2014-01-29 | 南京大学 | Supercapacitor electrode material preparation method based on three-dimensional graphene |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993056A (en) * | 2010-12-01 | 2011-03-30 | 天津大学 | Graphene-based porous macroscopic carbon material and preparation method thereof |
| CN102992308A (en) * | 2012-11-21 | 2013-03-27 | 复旦大学 | Graphene with high specific capacitance and preparation method thereof |
| CN103145125A (en) * | 2013-04-01 | 2013-06-12 | 兰州大学 | Preparation method for high adsorptivity three-dimensional self-assembly graphene |
| CN103253655A (en) * | 2013-04-15 | 2013-08-21 | 中国科学院宁波材料技术与工程研究所 | Compound graphene with scattering scale and preparation method thereof |
| CN103545121A (en) * | 2013-10-23 | 2014-01-29 | 南京大学 | Supercapacitor electrode material preparation method based on three-dimensional graphene |
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