CN104276565A - Preparation method of ultralight graphene elastic aerogel - Google Patents
Preparation method of ultralight graphene elastic aerogel Download PDFInfo
- Publication number
- CN104276565A CN104276565A CN201410337377.6A CN201410337377A CN104276565A CN 104276565 A CN104276565 A CN 104276565A CN 201410337377 A CN201410337377 A CN 201410337377A CN 104276565 A CN104276565 A CN 104276565A
- Authority
- CN
- China
- Prior art keywords
- preparation
- graphite oxide
- described step
- ultralight
- aerogel
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
- Colloid Chemistry (AREA)
Abstract
The invention provides a preparation method of an ultralight graphene elastic aerogel. The method comprises the following steps: mixing a graphite oxide aqueous solution with an aqueous solution of polyvinylpyrrolidone; forming a sol by physically connecting a functional group of a graphite oxide structural unit and polyvinylpyrrolidone by virtue of a binding effect; obtaining a graphene hydrogel by means of hydrothermal reaction reduction and self-assembly process; and freezing and drying the hydrogel to obtain the ultralight graphene elastic aerogel. The preparation method provided by the invention is simple, and the obtained ultralight graphene elastic aerogel has a continuous three-dimensional porous structure, an ultrahigh specific surface area, excellent elasticity and low density. In addition, when the elastic aerogel deforms, the conductivity reversibly changes correspondingly. Therefore, the prepared aerogel has a huge application prospect in adsorption and sensors.
Description
Technical field
The invention belongs to graphene aerogel preparation field, particularly a kind of preparation method of ultralight Graphene elasticity aerogel.
Background technology
Since within 2004, scientist successfully prepares Graphene, the two-dirnentional structure of its uniqueness and excellent performance are subject to the extensive concern of numerous scholar.Research shows, Graphene is made up of through SP2 hydridization carbon atom, present regular hexagon cycle honeycomb lattice structure, the Graphene thickness of individual layer is about 0.35nm, the Graphene of two dimension can pass through warpage, winding, the soccerballene forming zero dimension such as stacking, the carbon nanotube of one dimension and the graphite etc. of three-dimensional.Excellent mechanical property, electric property and the thermomechanical property of Graphene is widely used in energy storage, environmental protection, catalysis etc.
Aerogel is the porous nanometer material with low density and high-specific surface area.Aerogel has ultralight, abundant pore passage structure and high porosity, has excellent heat-proof quality.The framework material of aerogel has decisive action to its character.With Graphene as aerogel framework material, the two-dirnentional structure that Graphene is special and excellent physico-chemical property make the preparation of graphene aerogel and performance study receive publicity, the research of Graphene gel has following several usually: Graphene gel (Xu Y, et al.ACS nano, 2010,4:4324-4330), on this basis, gel (ChenZP, et al, the Nature materials that researcher fills at polymer, 2011,10,424-428), and inorganics filled aerogel is studied.Recent Research for Graphene elasticity aerogel has with oiliness organism microballoon for masterplate obtains uniform three dimensional pore passage structure (Li Y, et al.Advanced Materials, 2014).
At present, the preparation of aerogel adopts sol-gel method to prepare usually, by crosslinked obtain hydrogel after obtain aerogel through drying, for graphene aerogel, for making the aerogel of preparation, there is elasticity, the aperture of gel inside wants evenly regular, as passed through freezing treatment (the Qiu L to graphite oxide dispersion, et al.Nature communications, 2012,3:1241), and Zhejiang University will containing Graphene and carbon nanotube two kinds of nanomaterial solution carry out cryogenic freezing retain skeleton to prepare ultra-light elastic gel.But these methods obtain the condition harshness that elastic graphite alkene aerogel needs, and preparation flow is complicated, and cost is high.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of ultralight Graphene elasticity aerogel.Prepared Graphene elasticity aerogel, has stable deformation restorability, and the deformation simultaneously resistance of aerogel occurs to change accordingly.
A preparation method for ultralight Graphene elasticity aerogel, preparation method comprises:
(1) the preparation process of graphite oxide and polyvinylpyrrolidone colloidal sol
At room temperature, take graphite oxide adding distil water and be made into graphite oxide dispersion, ultrasonic uniformly solution; Take polyvinylpyrrolidone adding distil water and be made into polyvinylpyrrolidonesolution solution, ultrasonic disperse is even; By above two solution mixing, wherein the mass ratio of graphite oxide and polyvinylpyrrolidone is 10: 1 ~ 2: 3, the graphite oxide colloidal sol that then ultrasonic formation is uniform and stable;
(2) preparation of Graphene hydrogel
The stable sol obtained in (1) is added in water heating kettle, in an oven hydro-thermal reaction, naturally cooling, obtain cylindric hydrogel;
(3) preparation of Graphene elasticity aerogel
The hydrogel (2) obtained carries out freezing treatment, and obtains described Graphene elasticity aerogel through vacuum lyophilization.
The concentration of the graphite oxide dispersion in described step (1) is 1 ~ 10mg/mL.
In described step (1) is 60 ~ 300min to graphite oxide dispersion sonication treatment time.
The concentration of the polyvinylpyrrolidonesolution solution in described step (1) is 0.1 ~ 15mg/mL.
In described step (1) is 5 ~ 10min to polyvinylpyrrolidonesolution solution ultrasonic time.
The time ultrasonic to mixing solutions in described step (1) is 30 ~ 60min.
The temperature of the hydro-thermal reaction in an oven in described step (2) is 130 ~ 200 DEG C, and the treatment time is 5 ~ 20h.
The temperature freezing to hydrogel in described step (3) is-50 DEG C, and the time is 30 ~ 120min.
The temperature to hydrogel vacuum lyophilization in described step (3) is-50 DEG C, and the time is 18 ~ 48h, and vacuum tightness is 20 ~ 200Pa.
The ultralight Graphene elasticity aerogel of different performance is prepared by the content and ratio regulating graphite oxide and polyvinylpyrrolidone.
beneficial effect
(1) preparation technology of the present invention is simple, requires low to production unit;
(2) the ultralight Graphene elasticity aerogel prepared by the present invention has excellent mechanical property, repeatedly can compress and initial volume can be quickly recovered to, aerogel electroconductibility after hydrothermal reduction is good, its resistance changes along with the deformation of aerogel, can be used as elastic contactor.
(3) the ultralight Graphene elasticity aerogel internal gutter even structure prepared by the present invention, quality is light, and specific surface area is large, at drug loading, absorption toxic and harmful and can the aspect such as circuit element of deformation having broad application prospects.
Accompanying drawing explanation
Fig. 1 is the digital photograph of embodiment 1.
Fig. 2 is the Raman spectrogram of embodiment 1.
Fig. 3 is the time current curve of embodiment 1 in strain 60%.
Fig. 4 be embodiment 1 strain-time m-stress curve.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
At room temperature, take graphite oxide 120mg, be placed in the beaker of 100mL, then adding distil water 40mL is made into the dispersion liquid that graphite oxide concentration is 3mg/mL, then beaker is put into ultrasonic apparatus supersound process 1h; Under same room temperature, take polyvinylpyrrolidone 60mg, be placed in the beaker of 50mL, in beaker, add distilled water 20mL, supersound process 5min is carried out to polyvinylpyrrolidonesolution solution and obtains homodisperse polyvinylpyrrolidonesolution solution; Graphite oxide solution after above-mentioned ultrasonic disperse 1h mixed with polyvinylpyrrolidonesolution solution, magnetic agitation 5min, then continues supersound process 1h by mixed solution, obtains homodisperse colloidal sol 60mL; Scattered colloidal sol being poured into volume is in the water heating kettle liner of 80mL tetrafluoroethylene, then adds steel bushing, puts into the baking oven in advance temperature being raised to 180 DEG C, is hydro-thermal reaction 10h in an oven, turns off baking oven, naturally cool to room temperature; Open water heating kettle and obtain hydrogel, to the first freezing treatment 1h of hydrogel, the temperature of freezing treatment is-50 DEG C, then vacuum lyophilization process 48h, and in treating processes, vacustat is at about 50Pa.Fig. 1 is the digital photograph of ultralight Graphene elasticity aerogel prepared by the present embodiment, can find out: the quality of elasticity aerogel very light, calculating density is 0.025g/cm
3.Fig. 2 is the Raman spectrogram of elasticity aerogel prepared by the present embodiment, can find out: in figure, significantly bimodal (D peak and G peak) has obvious change, the ratio I of peak value before and after reduction
d/ I
gbe increased to 2.04 after reduction by 0.96 before reducing, show reduction reaction its structure is opened larger change, reduction degree is very large.Fig. 3 is the time current curve of elasticity aerogel when two ends making alive is 3V prepared by the present embodiment, the each peak value occurred shows that now elasticity aerogel is compressed 60%, can be clear and definite in figure find out that quantitative deformation occurs elastogel time, the multiple that the electrorheological of its correspondence is constant greatly, it can be said that this ultralight Graphene elasticity aerogel bright is when deformation, its resistance also changes.Fig. 4 to be diameter prepared by this example be cylindrical spring aerogel of 2.0cm strain-time m-stress curve, can find out from figure, during the every second compression 50% of elasticity aerogel can 100% return to original volume, and repeatedly this phenomenon rear can keep, can find out, during every second compression, the maximum stress of elastogel keeps stable value, shows that this elastogel can keep the stable of its mechanical property after repeatedly deformation.
Embodiment 2
At room temperature, take graphite oxide 240mg, be placed in the beaker of 100mL, then adding distil water 40mL is made into the dispersion liquid that graphite oxide concentration is 6mg/mL, then beaker is put into ultrasonic apparatus supersound process 1h; Under same room temperature, take polyvinylpyrrolidone 120mg, be placed in the beaker of 50mL, in beaker, add distilled water 20mL, supersound process 5min is carried out to polyvinylpyrrolidonesolution solution and obtains homodisperse polyvinylpyrrolidonesolution solution; Graphite oxide solution after above-mentioned ultrasonic disperse 1h mixed with polyvinylpyrrolidonesolution solution, magnetic agitation 5min, then continues supersound process 1h by mixed solution, obtains homodisperse colloidal sol 60mL; Scattered colloidal sol being poured into volume is in the water heating kettle liner of 80mL tetrafluoroethylene, then adds steel bushing, puts into the baking oven in advance temperature being raised to 180 DEG C, is hydro-thermal reaction 10h in an oven, turns off baking oven, naturally cool to room temperature; Open water heating kettle and obtain hydrogel, to the first freezing treatment 1h of hydrogel, the temperature of freezing treatment is-50 DEG C, then vacuum lyophilization process 48h, and in treating processes, vacustat is at about 50Pa.The elastogel obtained is tested, finds the sample in the relative example 1 of its intensity, increase, survey its Raman spectrum, the sample of reducing degree substantially and in example 1 can be observed and be consistent.
Embodiment 3
At room temperature, take graphite oxide 120mg, be placed in the beaker of 100mL, then adding distil water 40mL is made into the dispersion liquid that graphite oxide concentration is 3mg/mL, then beaker is put into ultrasonic apparatus supersound process 1h; Under same room temperature, take polyvinylpyrrolidone 60mg, be placed in the beaker of 50mL, in beaker, add distilled water 20mL, supersound process 5min is carried out to polyvinylpyrrolidonesolution solution and obtains homodisperse polyvinylpyrrolidonesolution solution; Graphite oxide solution after above-mentioned ultrasonic disperse 1h mixed with polyvinylpyrrolidonesolution solution, magnetic agitation 5min, then continues supersound process 1h by mixed solution, obtains homodisperse colloidal sol 60mL; Scattered colloidal sol being poured into volume is in the water heating kettle liner of 80mL tetrafluoroethylene, then adds steel bushing, puts into the baking oven in advance temperature being raised to 150 DEG C, is hydro-thermal reaction 10h in an oven, turns off baking oven, naturally cool to room temperature; Open water heating kettle and obtain hydrogel, to the first freezing treatment 1h of hydrogel, the temperature of freezing treatment is-50 DEG C, then vacuum lyophilization process 48h, and in treating processes, vacustat is at about 50Pa.The sample prepared by example 3 is compared with example 1, and the size of sample increases to some extent; Survey its Raman spectrum, can from I
d/ I
gfind out, in example 3, the reducing degree of sample is low compared with the sample in example 1.
Claims (9)
1. a preparation method for ultralight Graphene elasticity aerogel, comprising:
(1) at room temperature, take graphite oxide adding distil water and be made into graphite oxide dispersion, ultrasonic uniformly solution; Take polyvinylpyrrolidone adding distil water and be made into polyvinylpyrrolidonesolution solution, ultrasonic disperse is even; By above two solution mixing, wherein the mass ratio of graphite oxide and polyvinylpyrrolidone is 10: 1 ~ 2: 3, the graphite oxide colloidal sol that then ultrasonic formation is uniform and stable;
(2) stable sol obtained in (1) is added in water heating kettle, in an oven hydro-thermal reaction, naturally cooling, obtain cylindric hydrogel;
(3) hydrogel that (2) obtain is carried out freezing treatment, and obtain described Graphene elasticity aerogel through vacuum lyophilization.
2. the preparation method of a kind of ultralight Graphene elasticity aerogel according to claim 1, is characterized in that: the concentration of the graphite oxide dispersion in described step (1) is 1 ~ 10mg/mL.
3. the preparation method of a kind of ultralight Graphene elasticity aerogel according to claim 1, is characterized in that: in described step (1) is 60 ~ 300min to graphite oxide dispersion sonication treatment time.
4. the preparation method of a kind of ultralight Graphene elasticity aerogel according to claim 1, is characterized in that: the concentration of the polyvinylpyrrolidonesolution solution in described step (1) is 0.1 ~ 15mg/mL.
5. the preparation method of a kind of ultralight Graphene elasticity aerogel according to claim 1, is characterized in that: in described step (1) is 5 ~ 10min to polyvinylpyrrolidonesolution solution ultrasonic time.
6. the preparation method of a kind of ultralight Graphene elasticity aerogel according to claim 1, is characterized in that: the time ultrasonic to mixing solutions in described step (1) is 30 ~ 60min.
7. the preparation method of a kind of ultralight Graphene elasticity aerogel according to claim 1, is characterized in that: the temperature of the hydro-thermal reaction in an oven in described step (2) is 130 ~ 200 DEG C, and the treatment time is 5 ~ 20h.
8. the preparation method of a kind of ultralight Graphene elasticity aerogel according to claim 1, it is characterized in that: the temperature freezing to hydrogel in described step (3) is-50 DEG C, the time is 30 ~ 120min.
9. the preparation method of a kind of ultralight Graphene elasticity aerogel according to claim 1, is characterized in that: be-50 DEG C to the temperature of hydrogel vacuum lyophilization in described step (3), and the time is 18 ~ 48h, and vacuum tightness is 20 ~ 200Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410337377.6A CN104276565B (en) | 2014-07-16 | 2014-07-16 | A kind of preparation method of ultralight Graphene elasticity aeroge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410337377.6A CN104276565B (en) | 2014-07-16 | 2014-07-16 | A kind of preparation method of ultralight Graphene elasticity aeroge |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104276565A true CN104276565A (en) | 2015-01-14 |
| CN104276565B CN104276565B (en) | 2016-07-06 |
Family
ID=52251984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410337377.6A Active CN104276565B (en) | 2014-07-16 | 2014-07-16 | A kind of preparation method of ultralight Graphene elasticity aeroge |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104276565B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106672944A (en) * | 2016-12-15 | 2017-05-17 | 东华大学 | Graphene foam film, and preparation and application thereof |
| CN106809822A (en) * | 2017-01-22 | 2017-06-09 | 戴天元 | A kind of preparation method of super-elasticity graphene aerogel |
| CN107601463A (en) * | 2017-08-18 | 2018-01-19 | 济南大学 | A kind of graphene aerosol method for preparing microsphere based on microflow control technique |
| CN107706395A (en) * | 2017-10-30 | 2018-02-16 | 成都格莱飞科技股份有限公司 | A kind of preparation method of polyester/graphite alkene aerogel composite |
| CN109331751A (en) * | 2018-11-14 | 2019-02-15 | 武汉纺织大学 | The graphene-based aerogel material and preparation method thereof for having tough structure |
| CN110153162A (en) * | 2018-02-05 | 2019-08-23 | 山东佳星环保科技有限公司 | It is a kind of can efficient process petroleum desorption liquid graphite oxide aerogel preparation method |
| CN112090400A (en) * | 2020-07-24 | 2020-12-18 | 山西大同大学 | Preparation method and application of calcium hydroxide-loaded graphene aerogel composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413689A (en) * | 2013-07-19 | 2013-11-27 | 北京科技大学 | Method for preparing graphene aerogel and graphene/ metallic oxide aerogel |
| CN103537236A (en) * | 2013-10-22 | 2014-01-29 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene aerogel |
-
2014
- 2014-07-16 CN CN201410337377.6A patent/CN104276565B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413689A (en) * | 2013-07-19 | 2013-11-27 | 北京科技大学 | Method for preparing graphene aerogel and graphene/ metallic oxide aerogel |
| CN103537236A (en) * | 2013-10-22 | 2014-01-29 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene aerogel |
Non-Patent Citations (3)
| Title |
|---|
| SON TRUONG NGUYEN ET AL.: "Morphology control and thermal stability of binderless-graphene aerogels from graphite for energy storage applications", 《COLLOIDS AND SURFACES A: PHYSICOCHEM. ENG. ASPECTS》 * |
| WUFENG CHEN ET AL.: "In situ self-assembly of mildchemical reduction graphene for three-dimensional architectures", 《NANOSCALE》 * |
| 南京药学院药剂学教研组: "《药剂学（第二版）》", 31 May 1985 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106672944A (en) * | 2016-12-15 | 2017-05-17 | 东华大学 | Graphene foam film, and preparation and application thereof |
| CN106809822A (en) * | 2017-01-22 | 2017-06-09 | 戴天元 | A kind of preparation method of super-elasticity graphene aerogel |
| CN106809822B (en) * | 2017-01-22 | 2018-06-22 | 戴天元 | A kind of preparation method of super-elasticity graphene aerogel |
| CN107601463A (en) * | 2017-08-18 | 2018-01-19 | 济南大学 | A kind of graphene aerosol method for preparing microsphere based on microflow control technique |
| CN107706395A (en) * | 2017-10-30 | 2018-02-16 | 成都格莱飞科技股份有限公司 | A kind of preparation method of polyester/graphite alkene aerogel composite |
| CN110153162A (en) * | 2018-02-05 | 2019-08-23 | 山东佳星环保科技有限公司 | It is a kind of can efficient process petroleum desorption liquid graphite oxide aerogel preparation method |
| CN109331751A (en) * | 2018-11-14 | 2019-02-15 | 武汉纺织大学 | The graphene-based aerogel material and preparation method thereof for having tough structure |
| CN109331751B (en) * | 2018-11-14 | 2021-11-30 | 武汉纺织大学 | Graphene-based aerogel material with tough structure and preparation method thereof |
| CN112090400A (en) * | 2020-07-24 | 2020-12-18 | 山西大同大学 | Preparation method and application of calcium hydroxide-loaded graphene aerogel composite material |
| CN112090400B (en) * | 2020-07-24 | 2022-12-20 | 山西大同大学 | Preparation method and application of calcium hydroxide-loaded graphene aerogel composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104276565B (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104276565A (en) | Preparation method of ultralight graphene elastic aerogel | |
| Cai et al. | Facile synthesis of three-dimensional heteroatom-doped and hierarchical egg-box-like carbons derived from moringa oleifera branches for high-performance supercapacitors | |
| Yao et al. | In situ surface decoration of Fe3C/Fe3O4/C nanosheets: Towards bi-functional activated carbons with supercapacitance and efficient dye adsorption | |
| Liang et al. | Popcorn-derived porous carbon for energy storage and CO2 capture | |
| Luo et al. | Two-step synthesis of B and N co-doped porous carbon composites by microwave-assisted hydrothermal and pyrolysis process for supercapacitor application | |
| Shi et al. | Highly porous carbon with graphene nanoplatelet microstructure derived from biomass waste for high‐performance supercapacitors in universal electrolyte | |
| Cui et al. | Environmentally friendly bark-derived Co-Doped porous carbon composites for microwave absorption | |
| Sun et al. | Self-assembly of biomass derivatives into multiple heteroatom-doped 3D-interconnected porous carbon for advanced supercapacitors | |
| Liu et al. | Nickel-doped activated mesoporous carbon microspheres with partially graphitic structure for supercapacitors | |
| Zhu et al. | Dual tuning of biomass-derived hierarchical carbon nanostructures for supercapacitors: the role of balanced meso/microporosity and graphene | |
| Xu et al. | Dung beetle forewing-derived nitrogen and oxygen self-doped porous carbon for high performance solid-state supercapacitors | |
| Song et al. | A versatile N-doped honeycomb-like carbonaceous aerogels loaded with bimetallic sulfide and oxide for superior electromagnetic wave absorption and supercapacitor applications | |
| Zhu et al. | High‐performance supercapacitor electrode materials from chitosan via hydrothermal carbonization and potassium hydroxide activation | |
| Ding et al. | High-surface-area porous carbon flakes derived from boat-fruited sterculia seeds for high-energy-density aqueous symmetric supercapacitors | |
| Zhang et al. | A novel mesoporous carbon with straight tunnel-like pore structure for high rate electrochemical capacitors | |
| CN106115652B (en) | A kind of B and/or P, N codope perilla leaf porous carbon and preparation method thereof | |
| CN104998589A (en) | Preparation method for efficient oil absorption carbon aerogel material | |
| CN106946253B (en) | One kind being based on HNO3The preparation method of the high-specific-capacitance active carbon of hydrothermal oxidization modification | |
| CN103991864B (en) | A kind of preparation method of graphene aerogel | |
| CN104401987B (en) | A kind of preparation method of porous graphene elastic foam | |
| Tan et al. | Dulse‐derived porous carbon–polyaniline nanocomposite electrode for high‐performance supercapacitors | |
| Li et al. | Mesoporous carbon microspheres with high capacitive performances for supercapacitors | |
| Chen et al. | Fabrication and supercapacitive properties of hierarchical porous carbon from polyacrylonitrile | |
| Wang et al. | Activated green resources to synthesize N, P co-doped O-rich hierarchical interconnected porous carbon for high-performance supercapacitors | |
| Yang et al. | Ammonia-assisted semicarbonization: a simple method to introduce micropores without damaging a 3D mesoporous carbon nanonetwork structure |
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 |