CN103626151A - Preparation method of graphene/carbon composite material - Google Patents

Preparation method of graphene/carbon composite material Download PDF

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Publication number
CN103626151A
CN103626151A CN201310613596.8A CN201310613596A CN103626151A CN 103626151 A CN103626151 A CN 103626151A CN 201310613596 A CN201310613596 A CN 201310613596A CN 103626151 A CN103626151 A CN 103626151A
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graphene
matrix material
preparation
carbon matrix
carbon
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张泽汇
武培怡
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Fudan University
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Fudan University
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Abstract

The invention relates to a method for preparing a graphene/carbon composite material, the method is mainly characterized by comprising the following steps: generating hydrothermal carbon under hydrothermal condition by using natural compounds, cladding graphene oxide by using the hydrothermal carbon so as to prepare a carbon clad material of the graphene in situ. The method is simple and convenient to operate, environment-friendly, the used raw material is easy to obtain, the method has large-scale preparation potential and wide application prospect.

Description

A kind of preparation method of graphene/carbon matrix material
Technical field
The invention belongs to fine chemical technology field, be specifically related to a kind of preparation method of graphene/carbon matrix material.
Background technology
2005, the people such as Stankovich obtain graphite oxide graphite deep oxidation, then graphite oxide is carried out in water to supersound process, obtain mono-layer graphite oxide sheet (the Stankovich et al. that thickness is about 1nm, Stable aqueous dispersions of graphitic nanoplatelets via the reduction of exfoliated graphite oxide in the presence of poly (sodium 4-styrenesulfonate). Journal of Materials Chemistry, 16:155), Here it is graphene oxide.
In the last few years, because Graphene has large specific surface area, high electroconductibility, Graphene and derivative thereof are widely used in electrochemical field.2008, the condenser capactiance that the people such as Rodney S. Ruoff use the Graphene of chemically modified to prepare reached 135F/g(Stoller, M. D.; Park, S.; Zhu, Y.; An, J.; Ruoff, R. S., Graphene-Based Ultracapacitors. Nano Letters 2008,8 (10), 3498-3502.).After this, people to Graphene, the application in electrochemical field conducts extensive research.Yet because Graphene itself does not have regular vesicular structure, electrolytical transmission in electrical condenser and the storage of electric charge have been limited.
The people such as .Klaus Mullen in 2012 utilize silicon on Graphene surface, to introduce regular meso-hole structure, have prepared high efficiency electrical condenser (Wu, Z.-S.; Sun, Y.; Tan, Y.-Z.; Yang, S.; Feng, X.; Muellen, K., Three-Dimensional Graphene-Based Macro-and Mesoporous Frameworks for High-Performance Electrochemical Capacitive Energy Storage. Journal of the American Chemical Society 2012,134 (48), 19532-19535.).2013, Feng, the people such as X utilize the conjugated polymers of porous to introduce microvoid structure on the surface of Graphene, thereby have obtained having graphene composite material (Zhuang, the X. of good hydrogen reduction catalytic effect; Zhang, F.; Wu, D.; Forler, N.; Liang, H.; Wagner, M.; Gehrig, D.; Hansen, M. R.; Laquai, F.; Feng, X., Two-Dimensional Sandwich-Type, Graphene-Based Conjugated Microporous Polymers. Angewandte Chemie 2013,125 (37), 9850-9854).
Summary of the invention
The present invention proposes a kind of preparation method of simple, convenient, eco-friendly graphene/carbon matrix material, this method can be by adding the natural compoundss such as polysaccharide, under the condition of hydro-thermal, Formed is modified graphene oxide, thereby obtains having the graphene/carbon matrix material of vesicular structure.
Method of the present invention utilizes the natural compoundss such as polysaccharide to generate under hydrothermal condition to have the hydro-thermal carbon of large conjugated structure to be interacted and carried out compound with graphene oxide by π π, form sandwich structure, meanwhile, this layer of hydro-thermal carbon can also further stop the polymerization of Graphene.This layer of hydro-thermal carbon on Graphene surface, after pyroprocessing, form vesicular structure, and Graphene has given matrix material good electroconductibility on Graphene surface.
The method of preparing graphene/carbon matrix material that the present invention proposes, concrete steps are as follows:
In graphene oxide suspension, add natural compound even, mixed dispersion liquid is transferred to high-temperature water thermal response 30min ~ 12h in autoclave, then water-cooled or naturally cool to room temperature, can obtain the graphene composite material of sandwich type; Described graphene composite material is heat-treated 30min ~ 12h under high temperature inert gas atmosphere, obtains specific surface area large, the graphene/carbon matrix material that electroconductibility is high.
In the present invention, graphene suspension is joined in water or ethanol and is obtained by graphene oxide, or the graphene suspension of other processing of process.
In the present invention, described natural compound is the material that hydro-thermal reaction Formed can occur any kind, is specially in glucose, Mierocrystalline cellulose, chitin or egg albumen etc. any.
In the present invention, the ratio of described graphene oxide and natural compound, can regulate according to specific surface area and the purposes of the type of reacted natural compounds and required matrix material.
Utilize the graphene/carbon matrix material that preparation method of the present invention obtains to apply in preparing electrical condenser, electrode materials or sorbing material.
Method concrete operations of the present invention are very simple: only need be by natural compound such as the graphene oxide suspension disperseing and polysaccharide, be placed in hydrothermal reaction kettle, after temperature reaction several hours, be cooled to room temperature, dry again, then under inert atmosphere, pyroprocessing can obtain graphene/carbon matrix material.The device of hydro-thermal reaction can used at present commercial hydrothermal reaction kettle or equipment similarly.This working method is simply free from environmental pollution, has in a lot of fields application.
The graphene/carbon matrix material of preparing by the present invention, has uniform microvoid structure, can be applied to prepare electrode material of lithium battery, capacitance electrode active material and oxygen reduction reaction catalyzer etc.The present invention has certain value for the practical application of Graphene.
The inventive method can simply be prepared the graphene/carbon matrix material with sandwich type, the coated of carbon can be introduced vesicular structure on Graphene surface, thereby in a lot of fields as electrode materials, senser element, the field such as dye adsorption has a wide range of applications.This method is with low cost to be easy to get, and simple to operation, preparation process is easily controlled, and favorable reproducibility, and very environmental protection of preparation process are not polluted, and have very important using value.
Accompanying drawing explanation
Fig. 1: the outside drawing of matrix material prepared by chitosan and Graphene hydro-thermal;
Fig. 2: the TEM figure of matrix material prepared by chitosan and Graphene hydro-thermal;
Fig. 3: the SEM figure of matrix material prepared by chitosan and Graphene hydro-thermal;
Fig. 4: the outside drawing of matrix material prepared by Mierocrystalline cellulose and Graphene hydro-thermal;
Fig. 5: the TEM figure of matrix material prepared by Mierocrystalline cellulose and Graphene hydro-thermal;
Fig. 6: the SEM figure of matrix material prepared by Mierocrystalline cellulose and Graphene hydro-thermal;
Fig. 7: the SEM figure of matrix material prepared by glucose and Graphene hydro-thermal.
Embodiment
According to technical scheme of the present invention, choosing specific embodiment is described as follows:
embodiment 1:
The graphene oxide of 100mg is dispersed in the water of 20ml, adds the chitosan of 1g, mixed solution is transferred in autoclave, be warming up to 180 oc reacts 8h, is cooled to room temperature.After the black solid gel obtaining is dried, 600 othermal treatment 2h under the nitrogen atmosphere of C, can obtain doping nitrogen Graphene/hydro-thermal carbon composite of porous.
The optical photograph of product as shown in Figure 1, forms gel after Graphene and chitosan hydro-thermal.Fig. 2, the TEM that Fig. 3 is this matrix material and SEM figure, as can be seen from the figure, the carbon that chitin hydro-thermal generates is wrapped on Graphene, forms a kind of structure of sandwich type.
embodiment 2:
The graphene oxide of 200mg is dispersed in the water of 30ml, adds the Mierocrystalline cellulose of 2g, mixed solution is transferred in autoclave, be warming up to 220 oc reacts 8h, is cooled to room temperature.After the black solid gel obtaining is dried, 800 othermal treatment 1h under the nitrogen atmosphere of C, can obtain Graphene/hydro-thermal carbon composite of porous.
As Fig. 4, the optical photograph of product as shown in Figure 3, forms block black solid after Graphene and Mierocrystalline cellulose hydro-thermal.Fig. 5, the TEM that Fig. 6 is this matrix material and SEM figure, as can be seen from the figure, the carbon that Mierocrystalline cellulose hydro-thermal generates is wrapped on Graphene, forms a kind of tridimensional network of sandwich type.
embodiment 3:
The graphene oxide of 50mg is dispersed in the water of 15ml, adds the glucose of 1.5g, mixed solution is transferred in autoclave, be warming up to 180 oc reacts 8h, is cooled to room temperature.After the black solid gel obtaining is dried, 1000 othermal treatment 0.5h under the nitrogen atmosphere of C, can obtain Graphene/hydro-thermal carbon composite of porous.
Fig. 7 is the SEM figure of this matrix material, and in row figure, we can find out, the gel of generation has kept the tridimensional network of original Graphene substantially.

Claims (5)

1. the preparation method of a graphene/carbon matrix material, it is characterized in that its concrete steps are as follows: in graphene oxide suspension, add natural compound even, mixed dispersion liquid is transferred to high-temperature water thermal response 30min ~ 12h in autoclave, then water-cooled or naturally cool to room temperature, can obtain the graphene composite material of sandwich type; Described graphene composite material is heat-treated 30min ~ 12h under high temperature inert gas atmosphere, obtains specific surface area large, the graphene/carbon matrix material that electroconductibility is high.
2. the preparation method of graphene/carbon matrix material according to claim 1, is characterized in that graphene suspension is joined in water or ethanol and obtained by graphene oxide, or the graphene suspension of other processing of process.
3. the preparation method of graphene/carbon matrix material according to claim 1, it is characterized in that described natural compound is the material that hydro-thermal reaction Formed can occur any kind, be specially in glucose, Mierocrystalline cellulose, chitin or egg albumen etc. any.
4. the preparation method of graphene/carbon matrix material according to claim 1, the ratio that it is characterized in that described graphene oxide and natural compound, can regulate according to specific surface area and the purposes of the type of reacted natural compounds and required matrix material.
5. the graphene/carbon matrix material that preparation method obtains is as claimed in claim 1 applied in preparing electrical condenser, electrode materials or sorbing material.
CN201310613596.8A 2013-11-28 2013-11-28 Preparation method of graphene/carbon composite material Pending CN103626151A (en)

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Cited By (14)

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CN103979530A (en) * 2014-06-11 2014-08-13 安徽工业大学 Method for preparing porous carbon for electrochemical capacitor from egg white used as raw material
CN104167298A (en) * 2014-07-28 2014-11-26 复旦大学 Graphene-protein derived carbon supercapcaitor material and preparation method thereof
CN104466133A (en) * 2014-12-02 2015-03-25 中国科学院苏州纳米技术与纳米仿生研究所 Nitrogen-doped graphene carbon composite material and preparation method thereof
CN104772118A (en) * 2015-04-24 2015-07-15 河北工业大学 Hydrophilic graphene based carbon material and application thereof
WO2017018945A1 (en) * 2015-07-28 2017-02-02 Nanyang Technological University Electrode containing a hybrid nanomaterial of graphene oxide nanomaterial and cationic quaternized chitosan
CN107161980A (en) * 2017-05-24 2017-09-15 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 A kind of preparation method of the carbon nanosheet with graphene oxide fold pattern
WO2018001206A1 (en) * 2016-06-27 2018-01-04 济南圣泉集团股份有限公司 Graphene-based hierarchical porous capacitive carbon and preparation method therefor, and capacitor
CN108435134A (en) * 2018-05-10 2018-08-24 中南大学 The preparation and its application of egg white-graphene oxide self-assembled compound material
CN108520949A (en) * 2018-04-12 2018-09-11 广西中医药大学 A kind of graphene composite material and preparation method thereof
CN109786771A (en) * 2019-01-28 2019-05-21 西安科技大学 A kind of preparation method of N doping three-dimensional grapheme base fuel battery cathod catalyst
CN109847709A (en) * 2018-12-19 2019-06-07 浙江工业大学 A kind of luffa compound oil absorption material
CN110467175A (en) * 2019-09-19 2019-11-19 深圳烯创先进材料研究院有限公司 A kind of graphene enhances the preparation method of biomass porous carbon electromagnetic-wave absorbent
WO2020155708A1 (en) * 2019-01-31 2020-08-06 华南理工大学 Chitin/graphene composite sponge and preparation method and use thereof
CN112267209A (en) * 2020-09-23 2021-01-26 杨保成 Hydrophilic antibacterial non-woven fabric and preparation method thereof

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103979530A (en) * 2014-06-11 2014-08-13 安徽工业大学 Method for preparing porous carbon for electrochemical capacitor from egg white used as raw material
CN104167298A (en) * 2014-07-28 2014-11-26 复旦大学 Graphene-protein derived carbon supercapcaitor material and preparation method thereof
CN104466133A (en) * 2014-12-02 2015-03-25 中国科学院苏州纳米技术与纳米仿生研究所 Nitrogen-doped graphene carbon composite material and preparation method thereof
CN104772118A (en) * 2015-04-24 2015-07-15 河北工业大学 Hydrophilic graphene based carbon material and application thereof
CN104772118B (en) * 2015-04-24 2018-09-18 河北工业大学 A kind of hydrophilic graphene base carbon material and its application
WO2017018945A1 (en) * 2015-07-28 2017-02-02 Nanyang Technological University Electrode containing a hybrid nanomaterial of graphene oxide nanomaterial and cationic quaternized chitosan
WO2018001206A1 (en) * 2016-06-27 2018-01-04 济南圣泉集团股份有限公司 Graphene-based hierarchical porous capacitive carbon and preparation method therefor, and capacitor
CN107161980A (en) * 2017-05-24 2017-09-15 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 A kind of preparation method of the carbon nanosheet with graphene oxide fold pattern
CN108520949A (en) * 2018-04-12 2018-09-11 广西中医药大学 A kind of graphene composite material and preparation method thereof
CN108520949B (en) * 2018-04-12 2020-09-22 河北润东聚苯检验检测有限公司 Graphene composite material and preparation method thereof
CN108435134A (en) * 2018-05-10 2018-08-24 中南大学 The preparation and its application of egg white-graphene oxide self-assembled compound material
CN109847709A (en) * 2018-12-19 2019-06-07 浙江工业大学 A kind of luffa compound oil absorption material
CN109847709B (en) * 2018-12-19 2021-07-30 浙江工业大学 Luffa composite oil absorption material
CN109786771A (en) * 2019-01-28 2019-05-21 西安科技大学 A kind of preparation method of N doping three-dimensional grapheme base fuel battery cathod catalyst
WO2020155708A1 (en) * 2019-01-31 2020-08-06 华南理工大学 Chitin/graphene composite sponge and preparation method and use thereof
CN110467175A (en) * 2019-09-19 2019-11-19 深圳烯创先进材料研究院有限公司 A kind of graphene enhances the preparation method of biomass porous carbon electromagnetic-wave absorbent
CN112267209A (en) * 2020-09-23 2021-01-26 杨保成 Hydrophilic antibacterial non-woven fabric and preparation method thereof

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Application publication date: 20140312