CN106044752B - Preparation method of highly-oriented graphene aerogel - Google Patents
Preparation method of highly-oriented graphene aerogel Download PDFInfo
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- CN106044752B CN106044752B CN201610362004.3A CN201610362004A CN106044752B CN 106044752 B CN106044752 B CN 106044752B CN 201610362004 A CN201610362004 A CN 201610362004A CN 106044752 B CN106044752 B CN 106044752B
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Abstract
The invention discloses a high-orientation graphene aerogel and a preparation method thereof. The obtained highly-oriented graphene aerogel has high porosity, pores have high orientation degree along the direction of an electric field, and the pore size is controllable, so that the highly-oriented graphene aerogel can be used as electrode materials of batteries and super capacitors, electron field emission sources, heat insulation and dissipation materials, adsorption materials, high-flux water filtration materials, catalyst carriers and the like.
Description
Technical Field
The invention relates to the field of preparation of graphene aerogel, in particular to a preparation method of high-orientation graphene aerogel.
Background
Graphene (Graphene) is a monolayer two-dimensional crystal, has the highest strength of known materials and excellent electrical conductivity and thermal conductivity, is the most ideal two-dimensional nanomaterial at present, and has wide application prospects in the fields of materials, chemistry, biology, energy sources and the like. In 2010, Andre geom and konstatin novoseov, two professors of manchester university in the united kingdom, raised the worldwide hot trend of graphene research because of the first successful separation of stable graphene to obtain the nobel prize of physics. Macroscopic graphene aerogel is one of the main application forms of nano-scaled graphene. The graphene aerogel has the advantages of large specific surface area, good chemical stability and good electric and thermal conductivity and can be used as electrode materials of batteries and super capacitors, electron field emission sources, heat insulation and dissipation materials, adsorption materials, high-flux water filtration materials, catalyst carriers and the like.
The three-dimensional graphene aerogel can be prepared by methods such as a chemical vapor deposition method, an ice template method, a self-assembly method and a hydrothermal method. The chemical vapor deposition method highly depends on a metal template with a three-dimensional structure, has complex steps and complex operation, and is difficult to realize large-scale industrial preparation; the ice template method is a method for preparing aerogel by taking ice crystals in the freezing process of graphene or graphene oxide aqueous solution as a template; the self-assembly method and the hydrothermal method utilize the liquid crystallinity and the anisotropy of graphene to obtain the aerogel with a certain orientation degree under certain conditions.
The method lacks pretreatment and pre-orientation of a graphene dispersion system, and the structural order of the obtained product is poor. Preparing graphene aerogels with highly oriented structures remains a great challenge.
Disclosure of Invention
In view of the above problems in the prior art, the present applicant provides a method for preparing a highly oriented graphene aerogel. The highly-oriented graphene aerogel obtained by the invention has high porosity, very high orientation degree of pores along the direction of an electric field, controllable pore size, and can be used for electrode materials of batteries and super capacitors, electron field emission sources, heat insulation and dissipation materials, adsorption materials, high-flux water filtration materials, catalyst carriers and the like.
The technical scheme of the invention is as follows:
the applicant provides a preparation method of a high-orientation graphene aerogel, which comprises the following specific steps:
(1) mixing 1g of graphene with 20-100 g of water, and performing ultrasonic dispersion to obtain a graphene dispersion liquid;
(2) placing the graphene dispersion liquid prepared in the step (1) in a container with an electrode, and orienting the solution for 1-100 minutes by an external electric field to obtain a highly oriented graphene dispersion liquid; the frequency of the additional alternating electric field is 10-1000 Hz, and the strength is 50-5000V/m;
(3) and (3) continuously maintaining the electric field effect of the high-orientation graphene dispersion liquid obtained in the step (2), freezing and solidifying in liquid nitrogen, and further freezing and drying or critical freezing and drying to obtain the high-orientation graphene aerogel.
Preferably, the ultrasonic dispersion time in step (1) is: 10 to 100 minutes.
Preferably, in the step (2), the solution is oriented for 1-100 minutes by an external electric field to obtain a highly oriented graphene dispersion liquid; the frequency of the additional alternating electric field is 10-500 Hz, and the strength is 10-2000V/m.
The applicant also provides a preparation method of the highly-oriented graphene oxide aerogel, which comprises the following specific steps:
(1) mixing 1g of graphene oxide with 10-100 g of water, and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid;
(2) placing the graphene oxide dispersion liquid prepared in the step (1) in a container with an electrode, and orienting the solution for 1-100 minutes by an external electric field to obtain a highly oriented graphene oxide dispersion liquid; the frequency of the additional alternating electric field is 10-1000 Hz, and the strength is 50-5000V/m;
(3) and (3) continuously maintaining the electric field effect of the high-orientation graphene oxide dispersion liquid obtained in the step (2), freezing and solidifying in liquid nitrogen, and further freezing and drying or critical freezing and drying to obtain the high-orientation graphene oxide aerogel.
Reducing the high-orientation graphene oxide aerogel obtained in the step (3) through heat treatment to obtain an ordered porous graphene oxide aerogel; or reducing the highly-oriented graphene oxide aerogel obtained in the step (3) by using a chemical reducing agent, and washing and drying to obtain the ordered and porous graphene oxide aerogel.
Preferably, the ultrasonic dispersion time in step (1) is: 5-50 minutes.
Preferably, in the step (2), the solution is oriented for 1-100 minutes by an external electric field to obtain a highly oriented graphene dispersion liquid; the frequency of the additional alternating electric field is 10-500 Hz, and the strength is 10-2000V/m.
Preferably, the freeze drying or critical freeze drying time in step (3) is 2-40 h.
The reducing agent is selected from:
1-40% of hydrazine hydrate, 1-40% of sodium borohydride aqueous solution, 5-50% of vitamin C aqueous solution, 1-40% of glucose aqueous solution, 1-40% of hydroiodic acid aqueous solution, 1-40% of acetic acid aqueous solution, 1-40% of phenylhydrazine aqueous solution, 1-40% of hydrobromic acid aqueous solution, 1-40% of tea polyphenol aqueous solution, 1-40% of urea aqueous solution, 1-20% of sodium thiosulfate aqueous solution, 1-5% of sodium hydroxide aqueous solution and 1-40% of potassium hydroxide aqueous solution, Or 1-40% phenol water solution.
The beneficial technical effects of the invention are as follows:
(1) graphene or graphene oxide is used as a raw material, so that the method is suitable for large-scale industrial preparation;
(2) the preparation method fully utilizes the liquid crystal property of the graphene, is simple and convenient to operate, is green and environment-friendly, and does not need to add other auxiliary materials;
(3) the frequency and the intensity of an external electric field are controllable, and the orientation degree of the prepared graphene aerogel can be freely controlled;
(4) the density of the prepared high-orientation graphene aerogel can be adjusted, and the high-orientation graphene aerogel has good elasticity in the direction perpendicular to an orientation electric field and has excellent thermal conductivity and electrical conductivity.
Drawings
Fig. 1 is a schematic diagram of the principle of an electric field induced oriented graphene or graphene oxide dispersion;
fig. 2 is an electron scanning microscope photograph of a cross section of a graphene aerogel.
Detailed Description
The present invention will now be described in detail with reference to the accompanying drawings.
As shown in fig. 1, a three-dimensional graphene aerogel is prepared by using the responsiveness of graphene liquid crystal to an applied electric field.
The highly oriented graphene aerogel obtained by the method has the advantages that the graphene is oriented and arranged to form through holes along the direction of an electric field, and the density is 0.02-0.5g/cm3Compressive strength perpendicular to the direction of the orientation electric field1-15MPa, conductivity greater than 1000S/m, and porosity of 80-99.5%. The graphene aerogel with the macroporous through hole structure can be used as a structural material with a large surface area, is favorable for ion diffusion as an electrode material, can quickly adsorb and filter pollutants and keep large flux as a water treatment material, and can realize multiple functions by loading different object materials.
The present invention is described in detail with reference to the following embodiments, which are only used for further illustration of the present invention and are not to be construed as limiting the scope of the present invention, and the non-essential changes and modifications made by the person skilled in the art according to the above disclosure are all within the scope of the present invention.
Example 1:
(1) adding 1g of graphene and 6g of water, and carrying out ultrasonic treatment at 24 ℃ for 1 hour at 12KHz to obtain a graphene dispersion liquid;
(2) placing the graphene dispersion liquid obtained in the step (1) in a container with an electrode, and orienting the solution for 100 minutes by an external electric field with the frequency of 1000Hz and the strength of 2000V/m to obtain a highly oriented graphene dispersion liquid;
(3) continuously maintaining the electric field effect of the high-orientation graphene dispersion liquid obtained in the step (2), freezing and solidifying in liquid nitrogen, and further freezing and drying or critical freezing and drying for 40 hours to obtain the high-orientation graphene aerogel;
as shown in FIG. 2, in the obtained highly-oriented graphene aerogel, the graphene is oriented and arranged to form through holes along the direction of an electric field, and the density is 0.2g/cm3The compressive strength perpendicular to the direction of the orientation electric field is 15MPa, the orientation degree is more than 80%, the conductivity is more than 1000S/m, the porosity is 90%, the material can be used as a high-efficiency water treatment material, and the adsorption rate can reach 95% when the concentration of pollutants is lower than 20 mg/mL.
Example 2:
(1) adding 1g of graphene and 100g of water, and carrying out ultrasonic treatment at 60 ℃ for 10 hours at 5KHz to obtain a graphene dispersion liquid;
(2) placing the graphene dispersion liquid prepared in the step (1) in a container with an electrode, and orienting the solution for 80 minutes by an external electric field with the frequency of 50Hz and the strength of 1000V/m to obtain the highly oriented graphene dispersion liquid;
(3) continuously maintaining the electric field effect of the high-orientation graphene dispersion liquid obtained in the step (2), freezing and solidifying in liquid nitrogen, and further freezing and drying or critical freezing and drying for 3 hours to obtain the high-orientation graphene aerogel;
the obtained highly-oriented graphene aerogel has the graphene oriented arrangement to form through holes along the direction of an electric field, and the density of the highly-oriented graphene aerogel is 0.01g/cm3The compressive strength perpendicular to the orientation electric field direction is 1MPa, the orientation degree is more than 90 percent, the conductivity is more than 1000S/m, and the porosity is 99 percent.
Example 3:
(1) adding 1g of graphene oxide and 30g of water, and carrying out ultrasonic treatment at 40 ℃ and 10KHz for 5 hours to obtain a graphene oxide dispersion liquid;
(2) placing the graphene oxide dispersion liquid prepared in the step (1) in a container with an electrode, and orienting the solution for 50 minutes by an external electric field with the frequency of 500Hz and the strength of 2000V/m to obtain a highly oriented graphene oxide dispersion liquid;
(3) continuously maintaining the electric field effect of the high-orientation graphene oxide dispersion liquid obtained in the step (2), freezing and solidifying in liquid nitrogen, and further freezing and drying for 25 hours to obtain high-orientation graphene oxide aerogel;
(4) reducing the ordered porous graphene oxide aerogel obtained in the step (3) through heat treatment to obtain an ordered porous graphene oxide aerogel;
the obtained highly-oriented graphene aerogel has the graphene oriented arrangement to form through holes along the direction of an electric field, and the density of the highly-oriented graphene aerogel is 0.5g/cm3The compressive strength perpendicular to the orientation electric field direction is 6MPa, the orientation degree is more than 85 percent, the conductivity is more than 1000S/m, and the porosity is 95.8 percent.
Example 4:
(1) adding 1g of graphene oxide and 5g of water, and carrying out ultrasonic treatment at 35 ℃ for 1 hour at 15KHz to obtain a graphene oxide dispersion liquid;
(2) placing the graphene oxide dispersion liquid prepared in the step 1 in a container with an electrode, and orienting the solution for 75 minutes by an external electric field with the frequency of 50Hz and the strength of 2000V/m to obtain a highly oriented graphene oxide dispersion liquid;
(3) continuously maintaining the electric field effect of the high-orientation graphene oxide dispersion liquid obtained in the step (2), freezing and solidifying in liquid nitrogen, and further performing critical freeze drying for 25 hours to obtain high-orientation graphene oxide aerogel;
(4) and (4) placing the ordered porous graphene oxide membrane obtained in the step (3) in hydrazine hydrate with the mass fraction of 10% for reduction for 8 hours, and washing and drying to obtain the graphene porous ordered membrane.
The obtained highly-oriented graphene aerogel has the graphene oriented arrangement to form through holes along the direction of an electric field, and the density of the highly-oriented graphene aerogel is 0.03-0.07g/cm3The compressive strength perpendicular to the direction of the orientation electric field is 2-4MPa, the orientation degree is more than 85%, the conductivity is more than 1000S/m, the porosity is 94%, the material can be used as a high-efficiency water treatment material, and the adsorption rate can reach 98% when the concentration of pollutants is less than 20 mg/mL.
Claims (2)
1. A preparation method of a highly-oriented graphene aerogel is characterized by comprising the following specific steps:
(1) mixing 1g of graphene with 20-100 g of water, and performing ultrasonic dispersion to obtain a graphene dispersion liquid;
(2) placing the graphene dispersion liquid prepared in the step (1) in a container with an electrode, and orienting the solution for 1-100 minutes by an external alternating electric field to obtain a highly oriented graphene dispersion liquid; the frequency of the additional alternating electric field is 10-1000 Hz, and the strength is 50-5000V/m;
(3) continuously maintaining the electric field effect of the high-orientation graphene dispersion liquid obtained in the step (2), freezing and solidifying in liquid nitrogen, and further freezing and drying or critical freezing and drying to obtain the high-orientation graphene aerogel;
the ultrasonic dispersion time in the step (1) is as follows: 10 to 100 minutes.
2. A preparation method of high-orientation graphene oxide aerogel is characterized by comprising the following specific steps:
(1) mixing 1g of graphene oxide with 10-100 g of water, and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid;
(2) placing the graphene oxide dispersion liquid prepared in the step (1) in a container with an electrode, and orienting the solution for 1-100 minutes by an external alternating electric field to obtain a highly oriented graphene oxide dispersion liquid; the frequency of the additional alternating electric field is 10-1000 Hz, and the strength is 50-5000V/m;
(3) continuously maintaining the electric field effect of the high-orientation graphene oxide dispersion liquid obtained in the step (2), freezing and solidifying in liquid nitrogen, and further freezing and drying or critical freezing and drying to obtain the high-orientation graphene oxide aerogel;
reducing the high-orientation graphene oxide aerogel obtained in the step (3) through heat treatment to obtain an ordered porous graphene oxide aerogel; or reducing the highly-oriented graphene oxide aerogel obtained in the step (3) by using a chemical reducing agent, and washing and drying to obtain an ordered porous graphene oxide aerogel;
the reducing agent is selected from:
1-40% of hydrazine hydrate, 1-40% of sodium borohydride aqueous solution, 5-50% of vitamin C aqueous solution, 1-40% of glucose aqueous solution, 1-40% of hydroiodic acid aqueous solution, 1-40% of acetic acid aqueous solution, 1-40% of phenylhydrazine aqueous solution, 1-40% of hydrobromic acid aqueous solution, 1-40% of tea polyphenol aqueous solution, 1-40% of urea aqueous solution, 1-20% of sodium thiosulfate aqueous solution or 1-40% of phenol aqueous solution;
the ultrasonic dispersion time in the step (1) is as follows: 5-50 minutes;
the time of freeze drying or critical freeze drying in the step (3) is 2-40 h.
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| CN108262012A (en) * | 2018-01-24 | 2018-07-10 | 上海理工大学 | A kind of preparation method of graphene aerogel air purifying filter mesh |
| CN110857894B (en) * | 2018-08-24 | 2021-06-04 | 中山大学 | Flexible mechanical sensor capable of detecting stress direction based on ordered graphene and preparation method thereof |
| CN109320286B (en) * | 2018-11-14 | 2021-08-20 | 武汉纺织大学 | Magnetic graphene-based aerogel material with ordered structure and preparation method thereof |
| CN110010364B (en) * | 2019-04-28 | 2020-10-30 | 清华大学 | Graphene-based ordered high-density porous carbon and preparation method and application thereof |
| CN111204852B (en) * | 2020-01-17 | 2022-05-20 | 四川农业大学 | Livestock and poultry wastewater tail water treatment system |
| CN111591978A (en) * | 2020-05-29 | 2020-08-28 | 成都理工大学 | Preparation method for preparing graphene air filter element on large scale |
| WO2022120712A1 (en) * | 2020-12-10 | 2022-06-16 | 中国科学院深圳先进技术研究院 | Size-controllable aerogel ball and preparation method and application thereof |
| CN112852386B (en) * | 2021-01-25 | 2022-03-29 | 武汉科技大学 | High-orientation layered graphene aerogel phase-change composite material and preparation method thereof |
| CN114853502B (en) * | 2022-05-26 | 2023-05-12 | 哈尔滨工业大学（威海） | Ceramic/graphene aerogel wave-absorbing material and preparation method and application thereof |
| CN115341306B (en) * | 2022-09-23 | 2023-04-28 | 内蒙古大学 | Graphene aerogel fiber and preparation method thereof |
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| CN102239114A (en) * | 2008-12-04 | 2011-11-09 | 泰科电子公司 | Graphene and graphene oxide aerogels |
| CN103115238A (en) * | 2011-11-17 | 2013-05-22 | 浙江海洋学院 | Preparation method for depositing graphite lubricant coating with high consistent orientation under electric field induction |
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| CN102239114A (en) * | 2008-12-04 | 2011-11-09 | 泰科电子公司 | Graphene and graphene oxide aerogels |
| CN103115238A (en) * | 2011-11-17 | 2013-05-22 | 浙江海洋学院 | Preparation method for depositing graphite lubricant coating with high consistent orientation under electric field induction |
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Inventor after: Liu Zheng Inventor after: Wang Qinsheng Inventor after: Yang Yongqiang Inventor after: Liu Yuan Inventor after: Jin Ling Inventor after: Cheng Xiaobao Inventor before: Liu Zheng Inventor before: Wang Qinsheng Inventor before: Yang Yongqiang Inventor before: Liu Yuan Inventor before: Jin Ling Inventor before: Chen Xiaobao |
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