CN103834993A - Preparation method of graphene dendritic crystals and graphene dendritic crystals thereof - Google Patents
Preparation method of graphene dendritic crystals and graphene dendritic crystals thereof Download PDFInfo
- Publication number
- CN103834993A CN103834993A CN201410006530.7A CN201410006530A CN103834993A CN 103834993 A CN103834993 A CN 103834993A CN 201410006530 A CN201410006530 A CN 201410006530A CN 103834993 A CN103834993 A CN 103834993A
- Authority
- CN
- China
- Prior art keywords
- graphene
- dendrite
- electrode
- square wave
- dendritic crystals
- 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.)
- Pending
Links
Images
Abstract
The invention relates to a preparation method of graphene dendritic crystals and graphene dendritic crystals thereof. After a square wave electric signal is applied to two ends of an oxidized graphene solution, the duty ratio, frequency, and voltage are regulated to allow the actual current density to be higher than the limiting current density; the diffusion overpotential increases sharply; oxidized graphene particles are quite short near the electrodes; only part of the crystal face where the particles can reach continue to grow; the other part of the crystal face is passivated; whisker-like dendritic crystals grow on the electrodes, which are the graphene dendritic crystals. Compared with the prior art, the method of the invention allows the actual current density to be higher than the limiting current density by using square wave electrodeposition technology and through regulation of various process parameters, and discovers and prepares the graphene dendritic crystals for the first time. The graphene dendritic crystals have excellent electrical and mechanical properties. The invention has important theoretical and guiding significance on exploration and development of novel graphene derivative materials, and expansion of the application fields of graphene.
Description
Technical field
The invention belongs to Graphene derivative field, especially relate to a kind of preparation method and Graphene dendrite thereof of Graphene dendrite.
Background technology
Graphene is the carbon atomic layer with monatomic thickness, since 2004 come out, has caused widely and to have paid close attention at numerous areas, and they demonstrate in field application prospects widely such as optics, sensing, catalysis and electricity because of its unique physicochemical property.The Graphene derivative of exploring novel texture is the intrinsic performance of strengthening Graphene excellence and gives the Major Technology of its new function.In recent years, investigator has developed the technological method of a series of Graphene derivatives in succession, has prepared the Graphene derivative of the special and unique properties of various structures.The Graphene derivatives such as such as graphene fiber, graphene film/paper, foamy graphite, activation Graphene and Graphene gel.For fully optical, electrical, the magnetic property of exploitation Graphene excellence also need to explore the Graphene derivative of new excellent performance.
Dendrite refers to a kind of dendrite that has obvious trunk forming under the condition of far from equilibrium state, dendritic growth is a kind of general phenomenon of occurring in nature, natural snowflake is also the dendrite that crystallization occurs in oversaturated water vapour, and at pottery, in the optimization process of metallurgy and material, dendrite is just more general.In the process of dendritic growth, the direction of branch is the direction of crystallographic axis, and has repeatability, finally forms the resemblance of self similarity.In micro Nano material research, pine-tree structure material causes investigator's concern because having large specific surface area and overall electroconductibility at numerous areas such as optics, electromagnetism, Surface Physical Chemistry, catalysis.The further investigation of dendrite has important theoretical reference to exploitation type material and is worth.
Graphene dendrite is the one of Graphene derivative, up to the present, does not also see pertinent literature report.In traditional graphene oxide electrodeposition process, ignored the situation of extreme condition, only made the Graphene of film like, and the electricity of the Graphene of film like, mechanical property are weaker than Graphene dendrite.
Chinese patent CN103172058A has announced a kind of preparation method of three-dimensional netted Graphene, at the two ends of graphite oxide solution electrode insertion, for electrode applies after square wave electrical signal, graphite oxide will experience positive square-wave voltage absorption on same electrode, two processes of losing side wave voltage reduction, graphite oxide particle is adsorbed and reduces at electrode surface, and upwards grow with tree-shaped form, final accumulation forms three-dimensional netted Graphene, comprise the following steps: take natural flake graphite as raw material, prepare graphite oxide and be mixed with graphite oxide suspension; Electrode is inserted to the two ends of graphite oxide suspension; On electrode, connecting signal generator, is that electrode applies square wave electrical signal by signal generator, makes graphite oxide on same electrode, be adsorbed and reduce, and upwards grows with tree-shaped form, is finally deposited in together, forms three-dimensional netted Graphene.This patent reactant used is graphite oxide, in the situation that electric field produces concentration polarization overpotential, because reactant is graphite oxide, this particle is thicker, mechanical property is larger, and on electrode, being reduced to generate has relief three-dimensional arborescence, the i.e. structure of three-dimensional network.
Summary of the invention
Object of the present invention is exactly preparation method and the Graphene dendrite thereof that a kind of Graphene dendrite with excellent electricity, mechanical property is provided in order to overcome the defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions:
A kind of preparation method of Graphene dendrite, apply after square wave electrical signal at the two ends of graphene oxide solution, by dutycycle, frequency, the voltage of regulation and control square wave electrical signal, make the current density of the actual use current density that oversteps the extreme limit, anxious poly-increase of diffusion overpotential, near electrode by famine graphene oxide particle, only have the part crystal face that particle can reach can also continue to grow up, and another part crystal face is passivated, on electrode, with the dendrite material growth of palpus shape, be Graphene dendrite.
The method specifically comprises the following steps:
(1) the graphene oxide solution of preparation 1～2mg/ml;
(2) graphene oxide solution is poured in electrochemical, the spacing of electrode is 10～100mm;
(3) provide square wave electrical signal with signal generator for this electrochemical, regulating the voltage swing of square wave electrical signal is-100～100V, reaction times is 1～2min, frequency is 0.01～0.5Hz, make near the famine graphene oxide particle of electrode, only have the part crystal face that particle can reach can also continue to grow up, and another part crystal face is passivated, form shape as the dendritic settled layer of branch, be Graphene dendrite.
Described electrode is nickel electrode or stainless steel electrode.
As preferably, in step (3), regulating the frequency of square wave electrical signal is 0.1～0.2Hz.
Between described signal generator and electrode, be connected power amplifier, described power amplifier is connected with oscilloscope simultaneously.
The present invention adopts device to comprise reaction vessel, electrode, signal generator, power amplifier and oscilloscope.Wherein, reaction vessel is synthetic glass container.The model of signal generator is DG1022, produces square wave, and the variation range of frequency, at 0～20MHz, is mainly used to output signal and signal is input in power amplifier.The model of power amplifier is HVP-300A, and its range of regulation is 0～300V (peak value), be mainly used to output amplify after electrical signal, by voltage-drop loading to the electrode at graphite oxide solution two ends.Oscillographic model is DS1052E, is used for observing various unlike signal amplitudes over time.
A kind of Graphene dendrite that adopts aforesaid method to make.
Compared with prior art, in the present invention, the principle of electrocrystallization is applied in the electrochemical reaction of graphene oxide, utilize square wave electro-deposition techniques by the various processing parameters of regulation and control, make the current density of the actual use current density that oversteps the extreme limit, find first and made Graphene dendrite.And this Graphene dendrite has excellent electricity, mechanical property.The present invention has important theory and directive significance to the Application Areas of exploring development of new Graphene derivant material and expand Graphene.Graphene dendrite preparation method tool of the present invention has the following advantages:
1, because the particle of a graphite oxide can obtain thousands of graphene oxide particle by the effect of peeling off, and reactant of the present invention is graphene oxide, graphene oxide particle thickness is in 1nm left and right, the arborescence generating is one to the fractal dimension dendrite between two dimension, be Graphene dendrite, there is more excellent electricity and mechanical property compared to tridimensional network.
2, the method does not relate to poisonous chemical reagent, and this has been avoided causing structure deteriorate, environmental pollution and hazard to person etc.
3, device is simple, facility investment is few, and raw materials cost is cheap to be easy to get, processing ease, and favorable reproducibility, suitability is strong.
Accompanying drawing explanation
Fig. 1 is the present invention's device schematic diagram used;
Fig. 2 is the opticmicroscope figure of Graphene dendrite in embodiment 1;
Fig. 3 is the X-ray diffractogram of Graphene dendrite in embodiment 1;
Fig. 4 is the transmission electron microscope picture of Graphene dendrite in embodiment 1;
Fig. 5 is the high-resolution-ration transmission electric-lens figure of Graphene dendrite in embodiment 1;
Fig. 6 is the growing optics microscope figure of different time Graphene dendrite in embodiment 2;
Depositing time is followed successively by 20s by a to d, 30s, and 40s, 50s, scale is 100 μ m;
Fig. 7 is the high power transmission electron microscope picture that reacts the dendrite that 50s obtains in embodiment 2.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
In following examples, power amplifier adopts HVP-300A type power amplifier, and range of regulation is 0～300V (peak value), and signal generator is DG1022 type signal generator, the variation range of frequency is at 0～20MHz, and oscilloscope can adopt DS1052E type oscilloscope.
Embodiment 1
Adopt device as shown in Figure 1 to prepare Graphene dendrite, signal generator 1 connects power amplifier 2, power amplifier 2 connection electrode 4, wherein, power amplifier 2 is connected with the oscilloscope 3 that detects electrical signal frequency and waveform simultaneously, by signal generator 1, graphite oxide suspension 5 is applied to square-wave voltage.
In the present embodiment, the size of square-wave voltage is 80V, and frequency is 0.2Hz
The graphene oxide solution (GO) of preparation 1mg/ml; Two stainless steel electrodes (wide 10cm, long 10cm) are inserted in Glass Containers, form electrolyzer, two interelectrode distance 14mm; Select corresponding conditions (square wave, frequency is 0.2Hz, voltage 80V); The above-mentioned GO solution 120ml preparing is poured in Glass Containers, switch on power, reaction 100s, obtains Graphene dendrite.
From the opticmicroscope figure (Fig. 2) of Graphene dendrite, can see dendritic Graphene dendrite, similar with the pattern of metallic dendrite, there is obvious limb structure.In X-ray diffractogram (Fig. 3), graphene oxide locates respectively to have a strong and weak diffraction peak with 22.3 ° in 2 θ=11.2 °, corresponding to spacing 0.79nm and 0.398nm (according to Bragg equation 2d sin θ=n λ), react rear Graphene dendrite and located to occur a wide diffraction peak in 2 θ=23.9 °, be 0.372nm corresponding to Graphene dendrite basal spacing, it is large that the interlamellar spacing 0.335nm of the pure graphite of this numeric ratio wants, and proves that Graphene dendrite does not have accumulation again and forms graphite in reduction process.
With reference to figure 4, by the limb structure of having observed too Graphene dendrite under transmission electron microscope, with reference to figure 5, the dendrite interlamellar spacing obtaining under high power transmission electron microscope with under X-ray diffraction, obtain consistent, and on nanoscale, also there is fractal structure, embody the self-similarity feature of dendrite in different levels.
Embodiment 2
In the present embodiment, the size of square-wave voltage is 80V, and frequency is 0.1Hz
The graphene oxide solution (GO) of preparation 1mg/ml; Two stainless steel electrodes (wide 10cm, long 10cm) are inserted in Glass Containers, form electrolyzer, two interelectrode distance 14mm; Two stainless steel electrodes are connected with alternating field power supply, select corresponding conditions (square wave, frequency is 0.1Hz, voltage 80V); The above-mentioned GO solution 120ml preparing is poured in Glass Containers, switch on power, capture the differential responses time (in figure, the reaction times is followed successively by 20s, 30s, 40s, 50s), the opticmicroscope picture (Fig. 6) of Graphene dendrite.Along with the growth of time, Graphene dendrite is increasing as we can see from the figure.In the high power transmission electron microscope picture (Fig. 7) of the dendrite obtaining, also can see the fractal structure of Graphene dendrite from reaction 50s.
Embodiment 3
A kind of preparation method of Graphene dendrite, apply after square wave electrical signal at the two ends of graphene oxide solution, by dutycycle, frequency, the voltage of regulation and control square wave electrical signal, make the current density of the actual use current density that oversteps the extreme limit, anxious poly-increase of diffusion overpotential, near electrode by famine graphene oxide particle, only have the part crystal face that particle can reach can also continue to grow up, and another part crystal face is passivated, on electrode, with the dendrite material growth of palpus shape, be Graphene dendrite.The method specifically comprises the following steps:
(1) the graphene oxide solution of preparation 1.5mg/ml;
(2) graphene oxide solution is poured in electrochemical, electrode is nickel electrode, and the spacing of electrode is 10mm;
(3) provide square wave electrical signal with signal generator for this electrochemical, regulating the voltage swing of square wave electrical signal is 90V, reaction times is 1min, frequency is 0.01Hz, make near the famine graphene oxide particle of electrode, only have the part crystal face that particle can reach can also continue to grow up, and another part crystal face is passivated, form shape as the dendritic settled layer of branch, be Graphene dendrite.
Embodiment 4
A kind of preparation method of Graphene dendrite, apply after square wave electrical signal at the two ends of graphene oxide solution, by dutycycle, frequency, the voltage of regulation and control square wave electrical signal, make the current density of the actual use current density that oversteps the extreme limit, anxious poly-increase of diffusion overpotential, near electrode by famine graphene oxide particle, only have the part crystal face that particle can reach can also continue to grow up, and another part crystal face is passivated, on electrode, with the dendrite material growth of palpus shape, be Graphene dendrite.The method specifically comprises the following steps:
(1) the graphene oxide solution of preparation 2mg/ml;
(2) graphene oxide solution is poured in electrochemical, electrode is stainless steel electrode, and the spacing of electrode is 100mm;
(3) provide square wave electrical signal with signal generator for this electrochemical, regulating the voltage swing of square wave electrical signal is 100V, reaction times is 2min, frequency is 0.5Hz, make near the famine graphene oxide particle of electrode, only have the part crystal face that particle can reach can also continue to grow up, and another part crystal face is passivated, form shape as the dendritic settled layer of branch, be Graphene dendrite.
Claims (5)
1. the preparation method of a Graphene dendrite, it is characterized in that, apply after square wave electrical signal at the two ends of graphene oxide solution, by dutycycle, frequency, the voltage of regulation and control square wave electrical signal, make the current density of the actual use current density that oversteps the extreme limit, anxious poly-increase of diffusion overpotential, electrode is neighbouring by famine graphene oxide particle, only have the part crystal face that particle can reach can also continue to grow up, and another part crystal face is passivated, on electrode, with the dendrite material growth of palpus shape, be Graphene dendrite; Specifically comprise the following steps:
(1) the graphene oxide solution that compound concentration is 1～2mg/ml;
(2) graphene oxide solution is put into electrochemical, the spacing of electrode is 10～100mm;
(3) provide square wave electrical signal with signal generator for this electrochemical, regulating the voltage swing of square wave electrical signal is-100～100V, reaction times is 1～2min, frequency is 0.01～0.5Hz, make near the famine graphene oxide particle of electrode, only have the part crystal face that particle can reach can also continue to grow up, and another part crystal face is passivated, form shape as the dendritic settled layer of branch, be Graphene dendrite.
2. the preparation method of a kind of Graphene dendrite according to claim 1, is characterized in that, described electrode is nickel electrode or stainless steel electrode.
3. the preparation method of a kind of Graphene dendrite according to claim 1, is characterized in that, in step (3), regulating the frequency of square wave electrical signal is 0.1～0.2Hz.
4. the preparation method of a kind of Graphene dendrite according to claim 1, is characterized in that, between described signal generator and electrode, is connected power amplifier, and described power amplifier is connected with oscilloscope simultaneously.
5. a Graphene dendrite that adopts the arbitrary described method of claim 1～4 to make.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410006530.7A CN103834993A (en) | 2014-01-07 | 2014-01-07 | Preparation method of graphene dendritic crystals and graphene dendritic crystals thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410006530.7A CN103834993A (en) | 2014-01-07 | 2014-01-07 | Preparation method of graphene dendritic crystals and graphene dendritic crystals thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103834993A true CN103834993A (en) | 2014-06-04 |
Family
ID=50798876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410006530.7A Pending CN103834993A (en) | 2014-01-07 | 2014-01-07 | Preparation method of graphene dendritic crystals and graphene dendritic crystals thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103834993A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417525A (en) * | 2015-12-09 | 2016-03-23 | 东南大学 | Dendritic three-dimensional graphene and preparation method thereof |
| WO2018162708A1 (en) * | 2017-03-09 | 2018-09-13 | Kotman, Gerold | Conversion material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167313A (en) * | 2011-04-25 | 2011-08-31 | 同济大学 | Method for preparing graphene oxide through peeling in electric field |
| CN102491315A (en) * | 2011-12-08 | 2012-06-13 | 中国科学院化学研究所 | Method for preparing graphene |
| CN102963887A (en) * | 2012-11-30 | 2013-03-13 | 同济大学 | Electrochemistry stripping and reducing integrated graphene preparation method |
| CN103172058A (en) * | 2013-03-11 | 2013-06-26 | 同济大学 | Method for preparing three-dimensional netty graphene |
| WO2013130749A1 (en) * | 2012-02-28 | 2013-09-06 | Sila Nanotechnologies Inc. | Core-shell composites for sulfur-based cathodes in metal-ion batteries |
-
2014
- 2014-01-07 CN CN201410006530.7A patent/CN103834993A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167313A (en) * | 2011-04-25 | 2011-08-31 | 同济大学 | Method for preparing graphene oxide through peeling in electric field |
| CN102491315A (en) * | 2011-12-08 | 2012-06-13 | 中国科学院化学研究所 | Method for preparing graphene |
| WO2013130749A1 (en) * | 2012-02-28 | 2013-09-06 | Sila Nanotechnologies Inc. | Core-shell composites for sulfur-based cathodes in metal-ion batteries |
| CN102963887A (en) * | 2012-11-30 | 2013-03-13 | 同济大学 | Electrochemistry stripping and reducing integrated graphene preparation method |
| CN103172058A (en) * | 2013-03-11 | 2013-06-26 | 同济大学 | Method for preparing three-dimensional netty graphene |
Non-Patent Citations (4)
| Title |
|---|
| WENWEN FEI 等: "Dendritic graphene domains:Growth,morphology and oxidation promotion", 《MATERIALS LETTERS》 * |
| 刘艳云 等: "三维网状石墨烯的制备及其在超级电容器中的应用", 《储能科学与技术》 * |
| 刘艳云 等: "三维网状石墨烯的制备及其在超级电容器中的应用", 《储能科学与技术》, vol. 2, no. 5, 30 September 2013 (2013-09-30) * |
| 刘艳云 等: "石墨烯直径的动力学形成过程及其在柔性储能电极方面的应用", 《中国力学大会——2013年论文摘要集》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417525A (en) * | 2015-12-09 | 2016-03-23 | 东南大学 | Dendritic three-dimensional graphene and preparation method thereof |
| CN105417525B (en) * | 2015-12-09 | 2017-12-22 | 东南大学 | Dendritic crystalline three-dimensional grapheme and preparation method thereof |
| WO2018162708A1 (en) * | 2017-03-09 | 2018-09-13 | Kotman, Gerold | Conversion material |
| US10950775B2 (en) | 2017-03-09 | 2021-03-16 | Gerold Kotman | Conversion material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zheng et al. | Three-birds-with-one-stone electrolysis for energy-efficiency production of gluconate and hydrogen | |
| Sahoo et al. | Incorporation of carbon quantum dots for improvement of supercapacitor performance of nickel sulfide | |
| Xu et al. | Facilely hierarchical growth of N-doped carbon-coated NiCo2O4 nanowire arrays on Ni foam for advanced supercapacitor electrodes | |
| Naseri et al. | Microstructure, morphology and electrochemical properties of Co nanoflake water oxidation electrocatalyst at micro-and nanoscale | |
| Liu et al. | Iron oxide-based nanotube arrays derived from sacrificial template-accelerated hydrolysis: large-area design and reversible lithium storage | |
| Zhong et al. | Electrochemically controlled growth of silver nanocrystals on graphene thin film and applications for efficient nonenzymatic H2O2 biosensor | |
| Wang et al. | Controllable template synthesis of Ni/Cu nanocable and Ni nanotube arrays: a one-step coelectrodeposition and electrochemical etching method | |
| Chakarvarti | Track-etch membranes enabled nano-/microtechnology: A review | |
| CN108698849A (en) | Pass through the production of the graphene-based composite nanostructure of non-loading type graphene nano on piece growing zinc oxide nanorod or the micron bar acquisition in suspension | |
| Feng et al. | N-methylimidazole-assisted electrodeposition of Au porous textile-like sheet arrays and its application to electrocatalysis | |
| CN105565297B (en) | Graphene quantum dot and method prepared by electrochemical oxidation cutting carbon fiber tip surface | |
| Gan et al. | Investigation on chemical etching process of ZnO nanorods toward nanotubes | |
| CN105355462B (en) | A kind of δ-MnO2The preparation method and applications of thick film pseudocapacitors electrode | |
| CN108607586A (en) | A kind of method of nickel phosphide, preparation method and water electrolysis hydrogen production | |
| CN109989070A (en) | Three-dimensional classification FeP nanometer sheet Electrocatalytic Activity for Hydrogen Evolution Reaction material and its preparation method and application | |
| CN109261177A (en) | Nanoscale nickel phosphide/carbon cloth composite material and preparation method thereof and the application in elctro-catalyst | |
| Maile et al. | Facial growth of Co (OH) 2 nanoflakes on stainless steel for supercapacitors: effect of deposition potential | |
| Meseck et al. | Three-dimensional organization of surface-bound silicone nanofilaments revealed by focused ion beam nanotomography | |
| Illy et al. | Understanding the selective etching of electrodeposited ZnO nanorods | |
| CN103143369A (en) | Preparation of grapheme platinum/ copper nano grain multi-level nano structure material and application thereof | |
| Ji et al. | hui Wang | |
| CN109321948B (en) | Method for preparing silver nanorods by rapid green electrochemical method | |
| CN103834993A (en) | Preparation method of graphene dendritic crystals and graphene dendritic crystals thereof | |
| CN103320828B (en) | A kind of electrochemical preparation method of hexamethylenetetramine nanometer doped zinc oxide film | |
| CN111063550A (en) | Preparation method and application of hollow core-shell Fe-Co-based sulfide @ nickel hydroxide nanotube array |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140604 |
|
| RJ01 | Rejection of invention patent application after publication |