CN102161483B - Method for preparing graphene by heating organic solvent suspension of graphite oxide - Google Patents
Method for preparing graphene by heating organic solvent suspension of graphite oxide Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 43
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/23—Oxidation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a method for preparing graphene by heating organic solvent suspension of graphite oxide, relates to a chemical dispersion method for preparing the graphene, and belongs to the technical field of the preparation of the graphene. The method comprises the following steps of: (1) putting the graphite oxide into a polar organic solvent, and performing ultrasonic treatment for 2to 5 hours to obtain suspension at the mass concentration of between 0.01 and 10g/L; (2) heating the suspension in the step (1) for 4 to 24 hours until the suspension becomes black and is partially or entirely agglomerated; (3) performing suction-filtration on the black suspension in the step (2) to remove the polar organic solvent; and (4) dripping organic electrolyte solution into a filter cakeobtained in the step (3), filtering to obtain black paste, and directly coating the black paste on a detention body for use, or directly drying the filter cake obtained in the step (3) to obtain a graphene material. In the method, steps and instruments are simple, and the flow is suitable for large-scale production, so that an anhydrous graphene material with low price and high electric conductivity is obtained.
Description
Technical field
The present invention relates to the method that a kind of chemical dispersion method prepares Graphene, belong to the Graphene preparing technical field.
Background technology
The present invention relates to the method that the suspension of a kind of direct heating graphite oxide in organic solvent obtains grapheme material.Utilize good dispersion and the relatively high boiling point of these organic solvents and than low-steam pressure of graphite oxide in some organic solvent, but the suspension of direct heating graphite oxide, thus effectively remove oxygen-containing functional group on the graphite oxide.The grapheme material of the complete drying that obtains like this (anhydrous) has dispersiveness to a certain degree in organic solvent, can be directly used in some to the extremely sensitive device of moisture, in ultracapacitor or lithium ion battery.In addition, also can further remove organic solvent, obtain Graphene powdery or paper shape material.
Background technology
Graphene, English name Graphene is that carbon atom is arranged the Colloidal particles that forms according to hexagonal.As monolayer carbon atomic plane material, Graphene can obtain by peeling off graphite material.This graphite crystal film is after 2004 are found by the scientist of University of Manchester, and Graphene just becomes the focus that scientific circles and industry member are paid close attention to.The thickness of Graphene only has 0.335 nanometer, is not only in the known materials the thinnest a kind of, also very firmly hard; As simple substance, the speed that it at room temperature transmits electronics than known all conductor and semi-conductor all fast (in the Graphene travelling speed of electronics reached the light velocity 1/300).Because the weird atom structure of Graphene, wherein the behavior of current carrier (electronics and hole) must just can be described with relativistic quantum mechanics (relativistic quantum mechanics).Simultaneously, as the monolayer carbon atomic structure, the theoretical specific surface area of Graphene is up to 2630 m
2/ g.So high specific surface area is so that become extremely promising energy storage active material with the material based on Graphene, so that grapheme material might be applied at storage hydrogen, new type lithium ion battery, ultracapacitor or fuel cell.
At present, its preparation method has multiple, sends out (pasting HOPG), heating SiC method, metal substrate chemical Vapor deposition process, chemical dispersion method etc. such as slight rubbing manipulation or tear tape; Wherein, the most suitable large-scale industrialization of chemical dispersion method is produced grapheme material, and the scope of application is wider.
Particularly, graphite oxide is that graphite is at H
2SO
4, HNO
3, HClO
4Under the effect Deng strong acid and strong oxidizer, or under the electrochemistry peroxidation, after hydrolysis, form.Graphite oxide is a stratiform covalent compound equally, and it is 0.335nm that interfloor distance is approximately 0.8nm(graphite) different according to the preparation method.It is generally acknowledged, contain in the graphite oxide-C-OH ,-C-O-C, and-groups such as COOH.Different with graphite, because there is electrostatic repulsion in the existence of polar group between the oxidized graphite flake layer.Therefore, graphite oxide as peeling off under hyperacoustic effect, forms mono-layer graphite oxide alkene (graphene oxide) in external force in water or in other polar solvent.After making graphene oxide, make again greying of made graphene oxide deoxidation by reduction again, but its electroconductibility of recuperation section when keeping its how much patterns.
The method is dissociated into mono-layer graphite with natural graphite powder in oxidation and reduction process.Although be its electroconductibility of partial reduction (having destroyed Graphene high electron mobility character) in redox processes, its product has quite high Specific Surface Area Measurement (〉 700 m
2/ g), so the most suitable large-scale industrialization of the method is produced grapheme material.Yet because the existence of oxygen-containing functional group, graphite oxide and the monolithic Graphene electricity that is cleaved into thereof are led very low.For using mineral carbon alkene material in the relevant purposes of conduction, the investigator is constantly exploring various method of reducing, in the hope of improving the quality (mainly being electroconductibility) of redox graphene.At present, mainly contain following several method: hydrazine hydrate N2H4 H2O-100 reduction method shown in Figure 1, thermal treatment reduction method shown in Figure 2, microwave exposure reduction method shown in Figure 3.
Above several method of reducing have different characteristics.Wherein chemical reduction method can obtain graphene oxide reduction suspension afterwards, but its process is loaded down with trivial details, is unfavorable for scale operation.And used reductive agent wherein, have very large toxicity such as hydrazine hydrate, health of human body and environment protection have been consisted of larger threat.The thermal reduction method has fast and reduction ratio advantage more thoroughly; But because heating generally need to be carried out, increased the energy consumption of whole process under the high temperature more than 1000 degrees centigrade.And this method needs the comparison expensive device such as high-temperature heater.It is fast that the microwave exposure heating has speed, and cost is low, uses the characteristics such as simple.This process can be carried out in common microwave stove, and the irradiation oxidation graphite granule can obtain the fluffy graphene powder of black within one minute.But common microwave exposure carries out in air, and the Graphene that first reduction obtains very easily burns under microwave exposure even causes fire trouble, for the large-scale application of this method has been brought potential security threat.And the burning of Graphene has consumed the carbon in the product, so that ultimate yield is lower.In addition, the specific surface of the grapheme material that obtains with heat reduction and microwave reduction illustrates that usually less than 500 square metres of every grams grapheme material wherein is not individual layer, but has average 4～5 layers stacking.
And the application that a lot of electrochemistry are correlated with is such as ultracapacitor and the lithium ion battery of organic electrolyte, and is very responsive to moisture.Trace water divides and may be produced hydrogen and oxygen accumulation inside device by electrochemical decomposition, under certain conditions will catching fire or blast.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the defective that existing chemical dispersion method prepares Graphene, and a kind of cold operation, anhydrous, the Graphene chemical dispersion preparation method that is suitable for scale operation are provided.
Basic ideas of the present invention are, graphite oxide is dispersed in some anhydrous polar organic solvent, then utilize the high boiling point (relatively water) of organic solvent and than low-steam pressure, directly (temperature required in heat reduction) heats organic solvent suspension under lower temperature, thereby make monolithic graphene oxide deoxidation wherein, to recover its high conductivity.This has utilized the strong interaction of graphene oxide and polar organic solvent molecule, by organic solvent molecule intercalation cleavage graphite oxide to individual layer, then directly energy is passed to mono-layer graphite oxide alkene surface by the organic solvent molecule, thus the oxygen-containing functional group above removing.
Accordingly, concrete technical scheme provided by the invention is:
The organic solvent suspension of heated oxide graphite prepares the method for Graphene, comprises the steps, (1), graphite oxide is placed polar organic solvent, and ultrasonic 2～5 hours, get suspension, mass concentration is 0.01～10g/L; (2), with the suspension of step (1) heating 4～24 hours, become black to suspension, some or all of cohesion is arranged simultaneously; (3), the black suspension of step (2) is filtered the removal polar organic solvent; (4), in step (3) gained filter cake, splash into organic electrolyte solution and suction filtration, get black soup compound and directly coat the body of stopping over and use; Perhaps convection drying step (3) gained filter cake gets grapheme material.The described body of stopping over is the electrode of ultracapacitor or lithium cell.
Further, the electric dipole moment of described polar organic solvent molecule particularly, is propylene carbonate, dimethyl formamide or METHYLPYRROLIDONE greater than 2 debye.
Technical process of the present invention comprises the ultra-sonic dispersion of graphite oxide in organic solvent, low-temperature heat gained suspension, and follow-up separation and drying and other steps.Characteristics of the present invention are to utilize the polarity of functional group in the graphite oxide and the strong interaction between the polar organic solvent molecule, in the same medium, realize cleavage and the reduction of graphite oxide, effectively simplified production stage and prevented that other from polluting especially entering of water.The grapheme material conductance ratio graphite oxide of the complete drying that so obtains (anhydrous) exceeds 5 more than the magnitude, greater than 1S/m, and dispersiveness is to a certain degree arranged in organic solvent, can be directly used in some to the extremely sensitive device of moisture, in ultracapacitor or lithium ion battery.In addition, also can further remove organic solvent, obtain Graphene powdery or paper shape material.Step and instrument involved in the present invention are simple, and flow process is easy to scale operation, thus obtain cheap, the anhydrous grapheme material that the high electricity of holding concurrently is led.
Description of drawings
Accompanying drawing is used to provide a further understanding of the present invention, and consists of the part of specification sheets, is used for together with embodiments of the present invention explaining the present invention, is not construed as limiting the invention.In the accompanying drawings:
Shown in Figure 1 is the hydrazine hydrate N2H4 H2O-100 reduction method, and shown in Figure 2 is the thermal treatment reduction method, and shown in Figure 3 is the microwave exposure reduction method, and Fig. 4 is the schema that the present invention prepares the Graphene method.
Embodiment
Below in conjunction with accompanying drawing the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein only is used for description and interpretation the present invention, is not intended to limit the present invention.
Embodiment 1:
Utilization obtains the method for grapheme material at the propylene carbonate direct heating, comprises following preparation process:
1, takes by weighing 1g graphite oxide particle and place glass beaker, add the Carbon Dioxide propylene of 1L, use ultrasonic 2 hours of needle-like ultrasonic device, obtain the graphite oxide suspension of 1g/L;
2, the graphite oxide suspension that step 1 is obtained places oil bath to be heated with stirring to 150 degrees centigrade and kept 200 rev/mins of stirring velocitys 4 hours;
3, the suspension that step 2 is obtained is poured vacuum apparatus into, opens vacuum valve and carries out suction filtration, until dripless is dripped; After dripping electrolyte solution (the 1M TEA BF4/PC) washing of 1ml, suction filtration is 1 minute fast;
4, the slurry like material that step 3 is obtained is directly coated the ultracapacitor body of stopping over and is used as the organic ultracapacitor electrode.
Embodiment 2:
Utilization obtains the method for grapheme material at the propylene carbonate direct heating, comprises following preparation process:
1, takes by weighing 10g graphite oxide particle and place glass beaker, add the Carbon Dioxide propylene of 2L, use ultrasonic 5 hours of needle-like ultrasonic device, obtain the graphite oxide suspension of 5g/L;
2, the graphite oxide suspension that step 1 is obtained places oil bath to be heated with stirring to 150 degrees centigrade, and keeps 20 hours, 1000 rev/mins of stirring velocitys;
3, the suspension that step 2 is obtained is poured vacuum apparatus into, opens vacuum valve and carries out suction filtration, until dripless is dripped;
4,3 slurry like material that obtain are dried to get the Graphene powder material.
Embodiment 3:
Utilization direct heating in dimethyl formamide obtains the method for grapheme material, comprises following preparation process:
1, takes by weighing 7g graphite oxide particle and place glass beaker, add the anhydrous dimethyl formamide of 1L, use ultrasonic 2 hours of needle-like ultrasonic device, obtain the graphite oxide suspension of 7g/L;
2, the graphite oxide suspension that step 1 is obtained places oil bath to be heated with stirring to 150 degrees centigrade, and kept 15 hours, 200 rev/mins of stirring velocitys;
3, the suspension that step 2 is obtained is poured vacuum apparatus into, opens vacuum valve and carries out suction filtration, until dripless is dripped; After dripping electrolyte solution (the 1M TEA BF4/PC) washing of 1ml, suction filtration is 1 minute fast;
4, the electrode of 4 slurry like material that obtain directly being coated lithium cell uses as the organic ultracapacitor electrode.
Embodiment 4:
Utilization direct heating in METHYLPYRROLIDONE obtains the method for grapheme material, comprises following preparation process:
1, takes by weighing 10g graphite oxide particle and place glass beaker, add the anhydrous METHYLPYRROLIDONE of 1L, use ultrasonic 3 hours of needle-like ultrasonic device, obtain the graphite oxide suspension of 10g/L;
2, the graphite oxide suspension that step 1 is obtained places oil bath to be heated with stirring to 150 degrees centigrade, and kept 4 hours, 200 rev/mins of stirring velocitys;
3, the suspension that step 2 is obtained is poured vacuum apparatus into, opens vacuum valve and carries out suction filtration, until dripless is dripped;
4,3 slurry like material that obtain are directly dried to get paper shape and powder-mixed grapheme material.
It should be noted that at last: the above only is the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment the present invention is had been described in detail, for a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment puts down in writing, and perhaps part technical characterictic wherein is equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (2)
1. the organic solvent suspension of heated oxide graphite prepares the method for Graphene, it is characterized in that: comprise the steps:
(1) graphite oxide is dissolved in the propylene carbonate, ultrasonic 2-5 hour, get suspension, mass concentration is 0.01-10g/L;
(2) with the suspension of step (1) heating 4-24 hour, become black to suspension, some or all of cohesion is arranged simultaneously;
(3) black suspension of step (2) is filtered, remove propylene carbonate;
(4) in step (3) gained filter cake, splash into organic electrolyte solution and suction filtration, get the black soup compound and directly coat the collector use; Perhaps convection drying step (3) gained filter cake gets grapheme material.
2. the organic solvent suspension of heated oxide graphite according to claim 1 prepares the method for Graphene, it is characterized in that: described collector is the electrode of ultracapacitor or lithium cell.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100475863A CN102161483B (en) | 2011-02-28 | 2011-02-28 | Method for preparing graphene by heating organic solvent suspension of graphite oxide |
| PCT/CN2012/071069 WO2012116594A1 (en) | 2011-02-28 | 2012-02-13 | Graphene preparation method of heating organic solvent suspension of graphite oxide, and graphene prepared using said method and applications thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100475863A CN102161483B (en) | 2011-02-28 | 2011-02-28 | Method for preparing graphene by heating organic solvent suspension of graphite oxide |
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| Publication Number | Publication Date |
|---|---|
| CN102161483A CN102161483A (en) | 2011-08-24 |
| CN102161483B true CN102161483B (en) | 2013-04-24 |
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|---|---|
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| WO (1) | WO2012116594A1 (en) |
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| CN102161483B (en) * | 2011-02-28 | 2013-04-24 | 常州第六元素材料科技股份有限公司 | Method for preparing graphene by heating organic solvent suspension of graphite oxide |
| CN102496475B (en) * | 2011-11-16 | 2015-09-02 | 常州第六元素材料科技股份有限公司 | A kind of super capacitor electrode sheet based on Graphene and preparation method thereof |
| CN102496480B (en) * | 2011-12-16 | 2013-09-18 | 江南大学 | Preparation method of graphene/nickel-aluminum bi-metal hydroxide composite material and application thereof |
| CN104150469B (en) * | 2014-07-31 | 2015-07-15 | 山东玉皇新能源科技有限公司 | Method capable of preparing few-layer graphene powder in batches |
| CN106115676B (en) * | 2016-06-28 | 2018-11-20 | 常州第六元素材料科技股份有限公司 | A kind of graphene organic ink and preparation method thereof |
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| CN101927997A (en) * | 2009-06-25 | 2010-12-29 | 华东理工大学 | Method for preparation of graphene by liquid-phase reduction |
| CN101671015B (en) * | 2009-10-13 | 2011-07-20 | 南昌航空大学 | Method of producing graphene |
| CN101786620B (en) * | 2010-03-30 | 2011-12-28 | 武汉大学 | Method for chemical synthesis of graphene |
| CN101817516A (en) * | 2010-05-21 | 2010-09-01 | 哈尔滨工业大学 | Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping |
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| CN102161483B (en) * | 2011-02-28 | 2013-04-24 | 常州第六元素材料科技股份有限公司 | Method for preparing graphene by heating organic solvent suspension of graphite oxide |
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