CN104176728A - Preparation method for controlling graphene oxide nanostructure morphology - Google Patents
Preparation method for controlling graphene oxide nanostructure morphology Download PDFInfo
- Publication number
- CN104176728A CN104176728A CN201410145171.3A CN201410145171A CN104176728A CN 104176728 A CN104176728 A CN 104176728A CN 201410145171 A CN201410145171 A CN 201410145171A CN 104176728 A CN104176728 A CN 104176728A
- Authority
- CN
- China
- Prior art keywords
- nano structure
- graphene nano
- stannic oxide
- preparation
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a preparation method for controlling graphene oxide nanostructure morphology. The method comprises the following steps: carrying out ultrasonic dispersion of graphite oxide powder in deionized water to obtain a suspension with the concentration of 0.5-2.0mg/mL; adding 10-30mg of polyvinyl alcohol and NiCl2, and respectively carrying out ultrasonic treatment and magnetic stirring for 1h; reacting at a constant temperature of 120-200DEG C; and washing the above obtained product, and freeze-drying for above 5h. The method controls the self-assembling of graphene oxide nanosheets by introducing different amount of Ni<2+> and changing the temperature, and the main morphologies of the product comprise a single layer structure, a multilayer structure and a tridimensional network structure. The method overcomes the problem that the self-assembling of two-dimensional sheet-shaped nanomaterials, and a super capacitance material with a high capacitance value and stable charge and discharge performances is obtained. Compared with routine methods, the method has the advantages of simple device, easy operation, high yield and good controllability, and is of great significance for the self-assembling of the nanomaterials, performance optimization and mechanization.
Description
Technical field
The present invention relates to a kind of preparation method who controls stannic oxide/graphene nano structure and morphology, especially, for the preparation method of the different-shape stannic oxide/graphene nano structure of energy storage material.Adopt hydrothermal method, by introduce Ni in reaction soln
2+ion also regulates Ni
2+concentration and temperature of reaction realize the morphology control of nanostructure, and pattern mainly comprises individual layer, multilayer and three-dimensional netted.
Background technology
Graphene is by monolayer honeycomb shape hexagon sp
2the monatomic bed thickness two-dimensional material that hydridization carbon atom forms, has excellent electricity, heat conductivity and mechanical property.As the Yi Ge branch of Graphene, graphene oxide (being called for short GO) material normally utilizes strong oxidizer that natural graphite oxide powder oxidation is made, and abundant covalency oxygen-containing functional group and the defect in surface makes it have many potential application advantages.For example, high-density energy storage material; C catalyst efficient and with low cost; As high-efficient oxidant, be widely used in organic reaction system, comprise that olefin oxidation becomes polyester, methylenedioxy phenoxy changes into acetaldehyde and diarylmethanes is oxidized to ketone etc.; In addition, the existence of polarity oxygen-containing functional group makes GO have very strong wetting ability, causes it in multi-solvents (especially water), to show good dispersiveness, and this is extremely important for industrial application; These functional groups contribute to its finishing or functionalization.At present, GO nanostructure has been successfully applied to many fields such as microelectromechanical systems, biosensor and organizational project.
As energy storage material, the charge-discharge performance of GO is also subject to the impact of nanostructure size and pattern.The morphology control that realizes GO nanostructure has very important significance to its performance regulation and control and optimization.Yet the research work of this respect still rarely has report.Develop a kind of simple, economy and the large preparation method of the scope of application, for obtaining excellent capacitive property, have great importance.The invention discloses one step hydro thermal method technological line, by introducing the Ni of different amounts
2+ion and change temperature of reaction, reach the object of controlling GO nanometer sheet self-assembly behavior, thereby realize the pattern regulation and control of GO nanostructure, and product comprises individual layer, multilayer and tridimensional network.The method device is simple, easily operation, controllability are good, has very strong suitability.
Summary of the invention
Object of the present invention: a kind of preparation method who controls stannic oxide/graphene nano structure and morphology is provided, and main pattern comprises individual layer, multilayer and tridimensional network.The method is by introducing different amount Ni
2+with change temperature of reaction, reach the object of controlling GO nanometer sheet self-assembly behavior.This technology has overcome the unmanageable difficult problem of flake nano material self-assembly behavior, thereby realized, in a reaction system, prepare multiple different-shape stannic oxide/graphene nano structure, obtained and there is high capacity and the stable super capacitor material of charge-discharge performance; For controlled self-assembly, performance optimization and the device thereof of nano material provides a kind of new approach.
Technical scheme of the present invention: the Graphite Powder 99 of buying on market of take obtains graphite oxide powder as raw material adopts Hummer legal system; Get 20-40mg graphite oxide powder and join in deionized water, and ultrasonic dispersion obtains the suspension that concentration is 0.5-2.0mg/mL; Continuing, under ultrasonication, to add the NiCl of 10-30mg polyvinyl alcohol (PVA) and certain mass
2.6H
2o, mixing solutions is used respectively ultrasonic and magnetic agitation each 1 hour; Then mixing solutions is transferred in the polytetrafluoroethylliner liner of reactor, under a certain constant temperature within the scope of 120-200 ℃, reacted 10-16h; After reaction finishes, naturally cool to room temperature, product is through centrifugal, washing repeatedly, finally in freeze drier more than dry 5h.
1. as optimal selection, the temperature of reaction of preparing individual layer, multilayer stannic oxide/graphene nano structure is 120-150 ℃, and the temperature of reaction of preparing three-dimensional netted nanostructure is 160-200 ℃.
If when 2. hydrothermal temperature is lower than 120 ℃, there is the aggregate of graphene oxide in product.
3. in order to guarantee that suspended substance mixes, need to be respectively by ultrasonic and magnetic agitation each 1 hour.
4. as optimal selection, Ni
2+with the scope of graphite oxide powder mol ratio (r) be: do not add Ni
2+time, product is tridimensional network; R=0.02～0.10 o'clock, individual layer nanometer sheet; R=0.10～0.15 o'clock, multiple-layer overlapped nanostructure.
5. Ni
2+the amount that ion adds can not be too much, when 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 is through centrifugal, washing repeatedly, finally in freeze drier more than dry 5h.
Hydrothermal method has overcome the unmanageable difficult problem of flake nano material self-assembly behavior, has realized and in a reaction system, has prepared multiple different-shape stannic oxide/graphene nano structure; GO product has high thermostability and chemical stability, and performance can regulate and control in a big way, therefore in many fields such as micro-nano electronic mechanical system, energy storage and bio-sensings, has potential application prospect.
Beneficial effect of the present invention:
In conjunction with the advantage of hydrothermal method reaction, by introducing Ni
2+ion and adjusting temperature of reaction realize the morphology control of stannic oxide/graphene nano structure.Ni
2+the concentration of ion plays an important role to the morphology control of product.This method is easy to operate, prepared by product purity mass-producing higher and easily separated, that easily realize material.The optimization of morphology control such as capacitive property provides guarantee.
The preparation method that the present invention proposes has the following advantages:
(1) product has high thermostability and chemical stability;
(2) controllability is good.Only regulate Ni
2+concentration and hydrothermal temperature, realize the morphology control of stannic oxide/graphene nano structure.
(3) productive rate of product is high.
(4) performance is controlled.Because the performance height of GO nanostructure depends on pattern, thereby can in a big way, regulate and control.
(5) preparation method is simple, with low cost, has certain industrial applications prospect.
Accompanying drawing explanation:
Fig. 1 is the SEM figure of different-shape stannic oxide/graphene nano structure.(a-b) three-dimensional netted, (c) r=0.025, mono-layer graphite oxide alkene; (d) r=0.050, part mono-layer graphite oxide alkene; (e) r=0.100, the mixture of individual layer, multilayer graphene oxide; (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 differing temps, different Ni
2+xRD figure spectrum 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, scanning 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.
Embodiment
The preparation method who controls stannic oxide/graphene nano structure and morphology in the present invention, embodiment is as follows:
Embodiment 1
Three-dimensional netted GO nanostructure: utilize improved Hummer method, the Graphite Powder 99 bought on market of take makes graphite oxide powder as raw material; Get 30.2mg graphite oxide powder and join in deionized water, and ultrasonic dispersion obtains the suspension that concentration is 1.0mg/mL; Continuing, under ultrasonication, to add 20mg polyvinyl alcohol, mixing solutions is used respectively ultrasonic and magnetic agitation each 1 hour; Then mixing solutions is transferred in the polytetrafluoroethylliner liner of reactor, at 180 ℃, reacted 12h; After reaction finishes, naturally cool 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 tridimensional network, is to be interwoven in three-dimensional space by very thin nanometer sheet, forms a lot of holes.Because polyvinyl alcohol can infiltrate in the hole of three-dimensional netted graphene oxide, this nano structural material has good snappiness, the in the situation that of aggressive bend and torsion, can not rupture.
Embodiment 2
Temperature of reaction is 120 ℃, and other condition is with example 1.
Embodiment 2 products are the aggregate that pattern is irregular and size is very large.This is due at lower temperature, and the magnetism that π-π interaction produces, much larger than the repulsive force of random alignment, has caused the product of the tightly packed formation of stannic oxide/graphene nano sheet to form.This shows, temperature is during lower than 120 ℃, and the three-dimensional netted nanostructure of graphene oxide cannot obtain.
Embodiment 3
Ni
2+with graphite oxide powder mol ratio (r) be 0.025 o'clock, temperature of reaction is 120 ℃, other condition is with embodiment 1.
Embodiment 4
Ni
2+during with the mol ratio r=0.05 of presoma, other condition is with embodiment 3.
Embodiment 5
Ni
2+during with the mol ratio r=0.10 of presoma, other condition is with embodiment 3.
Embodiment 6
Ni
2+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, there is the obvious alternation from individual layer to multilayer in the pattern of stannic oxide/graphene nano structure.When r=0.025 (embodiment 3), product is evident as individual layer nanometer sheet (Fig. 1 c); When r=0.05 (embodiment 4), portion of product is mono-layer graphite oxide alkene, but still for individual layer nanometer sheet be main (Fig. 1 d); When r=0.1 (embodiment 5), product is the mixture (Fig. 1 e) of individual layer and multilayer stannic oxide/graphene nano structure; When r is increased to 0.15 (embodiment 6), product is all multilayer stannic oxide/graphene nano structure (Fig. 1 f).
Fig. 2 a is the TEM picture of the three-dimensional netted nanostructure of embodiment 1 acquisition.Due to high-temperature water thermal response, the nanostructure of paper accordion generates.The TEM picture (Fig. 2 b) amplifying shows, three-dimensional netted nanostructure has interconnected warp architecture, and edge rough.Illustration is the amplification TEM figure at edge, has confirmed that it is consisted of stannic oxide/graphene nano sheet.From Fig. 2 c-d, can find out, product has transparent laminate structure, and some folds appear at relatively coarse surface.The existence of these folds has reduced surperficial energy, is conducive to the stability of multilayered structure.Lip-deep fold has the height of 5-10nm.As shown in 2d illustration, carbon lattice fringe is easy to appear at fold place, and spacing is 0.38nm.
Fig. 3 is differing temps, different Ni
2+xRD figure spectrum with product under graphite oxide powder mol ratio (r) condition.Can see, they have similar XRD diffracting spectrum, and 25 ° of broad peaks of locating have confirmed that greying characteristic still keeps, and the intensity of this diffraction peak is along with the increase of r reduces gradually.When r=0.15 (embodiment 6), occurred corresponding to β-Ni (OH)
2(100), (101) and (102) diffractive features peak.This result shows, when the stannic oxide/graphene nano structure of preparation multilayer, and the Ni of introducing
2+ionic concn can not be too high, Ni
2+ion does not change component and the microtexture of product, just only the pattern of product is had to impact.
As shown in Figure 4, the electrode by three-dimensional netted stannic oxide/graphene nano structural modification has the highest quality than electric capacity (91.8F g
-1), the electrode that corresponding individual layer, multilayer graphene oxide are modified, its quality is respectively 59.6F g than the value of electric capacity
-1with 45.4F g
-1.Because quality is directly proportional to the specific surface area of capacitance material than capacitance, thus the quality of stannic oxide/graphene nano structure than capacitance, decline successively should be owing to specific surface area.The number of plies of graphene oxide (LN) can be calculated by LN=2620 * wt.%C/ specific surface area, wherein 2620 (m
2g
-1) be the theoretical specific surface area of mono-layer graphite oxide alkene, because graphene oxide exists Sauerstoffatom, LN can revise by carbon atom weight ratio (wt.%C), and specific surface area reduces with the increase of the number of plies, and multilayer stannic oxide/graphene nano structure has minimum specific surface area.
Fig. 5 has provided three electrodes that individual layer, multilayer and three-dimensional netted graphene oxide are modified, and quality is the variation tendency with charge/discharge rate (v) than capacitance.The quality of three electrodes than electric capacity at v=5V s
-1time be 352F g
-1, and at v=80V s
-1time be 78F g
-1.Yet, when v is from 5V s
-1be increased to 80V s
-1time three electrodes electric capacity all decline.Wherein, tridimensional network graphene oxide electrode has kept the highest quality than electric capacity in identical scope, and this may be because three-dimensional porous structure has accelerated the charge transfer in charge/discharge process.In addition, compare with individual layer, multilayer graphene oxide electrode, three-dimensional netted graphene oxide electrode has higher initial mass than electric capacity, and this is because it has higher specific surface area, and the close-packed single layer structure existing in multilayer graphene oxide has hindered effective charge transfer process.Particularly, the quality that three-dimensional netted nanostructure graphene oxide electrode shows is better than maximum (the v=5V s of report recently than capacitance
-1time, 220F g
-1).
Claims (6)
1. a preparation method who controls stannic oxide/graphene nano structure and morphology, is characterized in that, adopts hydrothermal method, by introduce Ni in reaction soln
2+ion also regulates Ni
2+with graphite oxide powder mole when hydrothermal temperature realize the morphology control of stannic oxide/graphene nano structure, pattern mainly comprises individual layer, multilayer and three-dimensional netted.Concrete steps are: the Graphite Powder 99 of buying on market of take obtains graphite oxide powder as raw material adopts Hummer legal system; Get 20-40mg graphite oxide powder and join in deionized water, and ultrasonic dispersion obtains the suspension that concentration is 0.5-2.0mg/mL; Continuing, under ultrasonication, to add the NiCl of 10-30mg polyvinyl alcohol (PVA) and certain mass
26H
2o, mixing solutions is used respectively ultrasonic and magnetic agitation each 1 hour; Then mixing solutions is transferred in the polytetrafluoroethylliner liner of reactor, under a certain constant temperature within the scope of 120-200 ℃, reacted 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. according to a kind of preparation method who controls stannic oxide/graphene nano structure and morphology described in claims 1, it is characterized in that, in order to guarantee that suspended substance mixes, add mixing solutions after PVA need to be respectively by ultrasonic and magnetic agitation each 1 hour.
3. according to a kind of preparation method who controls stannic oxide/graphene nano structure and morphology described in claims 1, it is characterized in that, the concentration of graphite oxide powder suspension is 0.5-2.0mg/mL, and PVA addition is 10-30mg.
4. according to a kind of preparation method who controls stannic oxide/graphene nano structure and morphology described in claims 1, it is characterized in that Ni
2+with the optimum range of graphite oxide powder mol ratio (r) be: during 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; Ni
2+the amount that ion adds can not be too much, when r>0.15, can generate β-Ni (OH)
2impurity.
5. according to a kind of preparation method who controls stannic oxide/graphene nano structure and morphology described in claims 1, it is characterized in that, the optimal reaction temperature of individual layer, multilayer stannic oxide/graphene nano structure is 120-150 ℃, and three-dimensional netted nanostructure optimal reaction temperature is 160-200 ℃.
6. according to a kind of preparation method who controls stannic oxide/graphene nano structure and morphology described in claims 1, it is characterized in that, the hydro-thermal reaction time of different-shape stannic oxide/graphene nano structure is 10-16h; Product is through centrifugal, washing repeatedly, finally in freeze drier more than dry 5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410145171.3A CN104176728B (en) | 2014-04-11 | 2014-04-11 | A kind of preparation method who controls stannic oxide/graphene nano structure and morphology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410145171.3A CN104176728B (en) | 2014-04-11 | 2014-04-11 | A kind of preparation method who controls stannic oxide/graphene nano structure and morphology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104176728A true CN104176728A (en) | 2014-12-03 |
| CN104176728B CN104176728B (en) | 2016-05-18 |
Family
ID=51958121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410145171.3A Expired - Fee Related CN104176728B (en) | 2014-04-11 | 2014-04-11 | A kind of preparation method who controls stannic oxide/graphene nano structure and morphology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104176728B (en) |
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 |
-
2014
- 2014-04-11 CN CN201410145171.3A patent/CN104176728B/en not_active Expired - Fee Related
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104176728B (en) | 2016-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Low et al. | Recent development of mixed transition metal oxide and graphene/mixed transition metal oxide based hybrid nanostructures for advanced supercapacitors | |
| Kumaraguru et al. | Reduced graphene oxide-wrapped micro-rod like Ni/Co organic-inorganic hybrid nanocomposite as an electrode material for high-performance supercapacitor | |
| Liang et al. | Hierarchical NiCo2O4 nanosheets@ halloysite nanotubes with ultrahigh capacitance and long cycle stability as electrochemical pseudocapacitor materials | |
| Zhang et al. | NiMn layered double hydroxide nanosheets in-situ anchored on Ti3C2 MXene via chemical bonds for superior supercapacitors | |
| Lin et al. | Research progress of MXenes and layered double hydroxides for supercapacitors | |
| Xiong et al. | Genuine unilamellar metal oxide nanosheets confined in a superlattice-like structure for superior energy storage | |
| Ashritha et al. | A review on Graphitic Carbon Nitride based binary nanocomposites as supercapacitors | |
| Chen et al. | Controllable Fabrication of Amorphous Co Ni Pyrophosphates for Tuning Electrochemical Performance in Supercapacitors | |
| Wang et al. | Electrode materials for aqueous asymmetric supercapacitors | |
| CN106698430B (en) | A kind of poly-dopamine is as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof | |
| CN104538595B (en) | Embedded nano metal load type carbon nano-sheet lithium ion battery negative material and its preparation method and application | |
| El-Deen et al. | Graphene wrapped MnO2-nanostructures as effective and stable electrode materials for capacitive deionization desalination technology | |
| Tao et al. | Nickel/cobalt layered double hydroxide hollow microspheres with hydrangea-like morphology for high-performance supercapacitors | |
| Xia et al. | Core-shell composite of hierarchical MoS2 nanosheets supported on graphitized hollow carbon microspheres for high performance lithium-ion batteries | |
| Xiao et al. | 3D hierarchical Co3O4 twin‐spheres with an urchin‐like structure: large‐scale synthesis, multistep‐splitting growth, and electrochemical pseudocapacitors | |
| Zhu et al. | Porous CoO nanostructure arrays converted from rhombic Co (OH) F and needle-like Co (CO3) 0.5 (OH)· 0.11 H2O and their electrochemical properties | |
| Liu et al. | Self-assembled porous hierarchical-like CoO@ C microsheets transformed from inorganic–organic precursors and their lithium-ion battery application | |
| CN104815637B (en) | Method for hydrothermal method preparation of graphene-loaded flower-type titanium dioxide composite material | |
| Lin et al. | Layered double hydroxides as electrode materials for flexible energy storage devices | |
| Li et al. | Fabrication of 2D/2D nanosheet heterostructures of ZIF-derived Co 3 S 4 and gC 3 N 4 for asymmetric supercapacitors with superior cycling stability | |
| Sun et al. | Influence of OH− and SO42− anions on morphologies of the nanosized nickel hydroxide | |
| Li et al. | Controlled synthesis and enhanced electrochemical performance of self-assembled rosette-type Ni-Al layered double hydroxide | |
| Cheng et al. | Robust growth of herringbone carbon nanofibers on layered double hydroxide derived catalysts and their applications as anodes for Li-ion batteries | |
| Xiao et al. | High-performance lithium storage achieved by chemically binding germanium nanoparticles with N-doped carbon | |
| Wang et al. | SnO2@ reduced graphene oxide composite for high performance lithium-ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160518 Termination date: 20170411 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |