CN103145124B - High-performance graphene paper and preparation method thereof - Google Patents
High-performance graphene paper and preparation method thereof Download PDFInfo
- Publication number
- CN103145124B CN103145124B CN201310101522.6A CN201310101522A CN103145124B CN 103145124 B CN103145124 B CN 103145124B CN 201310101522 A CN201310101522 A CN 201310101522A CN 103145124 B CN103145124 B CN 103145124B
- Authority
- CN
- China
- Prior art keywords
- graphene paper
- graphene
- preparation
- mentioned
- paper
- 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.)
- Expired - Fee Related
Links
Abstract
The invention relates to a graphene paper with excellent overall performance and a preparation method thereof for solving the problem that the mechanical property and the conductivity of the graphene paper in the present preparation technique are hard to improve simultaneously. The invention provides a simple method for preparing high-performance graphene paper, which comprises the following steps of: firstly, using a two-step chemical reduction method to obtain high-conductivity graphene powder, then putting the prepared high-conductivity graphene powder into a mold, and performing thermal-treatment molding at 100-900 DEG C under a pressure of 1-10 Mpa in certain vacuum, argon or hydrogen environment, and thus obtaining a graphene paper with excellent mechanical property and conductivity both. The mechanical strength and conductivity of the graphene paper are both higher than that of the present reported graphene paper, and the graphene paper disclosed by the invention have great application prospect in all fields of electromagnetic shielding, electrode material, high radiation, corrosion resistance, wear resisting material and the like as a structure and function integrated material.
Description
Technical field
The present invention relates to Graphene and preparation method thereof, particularly a kind of High-performance graphene paper and preparation method thereof and application.
Background technology
Graphene is nano material thin, the hardest in the world at present, is almost transparent, and only absorb the light of 2.3%, thermal conductivity is 5300W/mK, higher than CNT (carbon nano-tube) and diamond, and electronic mobility > 15000cm under normal temperature
2/ Vs, be greater than CNT (carbon nano-tube) and silicon crystal, and resistivity only has 10
-6Ω cm, also lower than copper, silver, for the material that current resistivity is minimum, be with a wide range of applications in Novel electronic devices, matrix material, solar cell, super capacitor, the hydrogen storage material etc. such as nanometer electronic device and unicircuit, flexible electronic device, ultra-high sensitive senser element in future.Although grapheme material has the characteristic of above excellence, at present application is less, and one of subject matter is difficult to obtain the Graphene self-supported membrane material that mechanical property and conductivity optimize simultaneously.Gordon G.Wallace is at Adv.Mater(2008,20,3557 – 3561), filtration under diminished pressure is adopted to obtain the graphene film (thickness is 6.0 μm) of self-supporting, i.e. graphene paper, after pyroprocessing, (electric conductivity is 351Scm to obtained graphene paper mechanical strength (tensile strength is 293.3MPa) with conductivity
-1) higher.But, aforesaid method prepares mechanical property and conductivity and theoretical value and also falls far short, and the graphene paper that above-mentioned preparation method obtains is not suitable for suitability for industrialized production, be difficult to be applied at actual product, be necessary to find simple method, realize the extensive preparation of graphene paper, and obtain the graphene paper of mechanical property and conductivity excellence.
Summary of the invention
Being difficult to prepare the excellent graphene paper problem of over-all properties (mechanical property and conductivity) in enormous quantities for solving in prior art to exist, the invention provides a kind of preparation method that can prepare High-performance graphene paper in enormous quantities.
The present invention adopts following technical scheme to realize:
A kind of High-performance graphene paper, it is characterized in that, described graphene paper is that the pure graphene powder hot pressing of employing two step chemical preparation obtains.
Described graphene paper, its thickness is 500nm ~ 5mm, and electric conductivity is 260 ~ 1350S/cm, and mechanical stretch intensity is 180 ~ 950Mpa, and Young's modulus is 45 ~ 110Gpa.
The present invention provides a kind of preparation method of High-performance graphene paper simultaneously, and its step is as follows:
(1) under condition of ice bath, 1.0g ~ 5g graphite is joined in the vitriol oil of 50 ~ 200ml, violent stirring 20 ~ 40min; Further by 8g ~ 20g KMnO
4join in above-mentioned mixed solution, violent stirring 20 ~ 40min; Above-mentioned mixed solution is transferred in 10 DEG C ~ 30 DEG C water-baths, slowly add 10g ~ 30gNaNO
3, stir 40min ~ 80min; Under agitation, 100ml ~ 300ml deionized water is joined continuously in above-mentioned mixed solution, then transferred in the oil bath of 60 DEG C ~ 100 DEG C of temperature, stir 20 ~ 40min time; Dropwise add 10ml ~ 40mlH again
2o
2, continue reaction 40min ~ 80min until solution becomes glassy yellow from dark-brown;
(2) under stirring environment, in above-mentioned glassy yellow graphene oxide solution, drip hydrazine hydrate and the PVP mixing solutions of 10ml ~ 40ml, at 40 DEG C ~ 80 DEG C temperature, react 30min ~ 2h; In above-mentioned solution, drip 20ml also original reagent further, continue reaction 20 ~ 60min, the black powder be precipitated; By centrifugal for above-mentioned powder, with water cleaning, repeats 2 times, then centrifugal again, with ethanol purge 1 time, to be less than at 50 DEG C drying 24 hours;
(3) join in mould by a certain amount of above-mentioned dried graphene powder, under the hot pressing environment that certain pressure, certain atmosphere surrounding and temperature are formed, mold pressing certain hour, can prepare thickness and the controlled graphene paper of area.
The preparation method of described graphene paper, described in step (2), the concentration of the PVP aqueous solution is 1 ~ 15wt%.
The preparation method of described graphene paper, going back original reagent described in step (2) is acetic acid or hydroiodic acid HI.
The preparation method of described graphene paper, the concentration of aqueous solution going back original reagent described in step (2): acetic acid is 10 ~ 30wt%, hydroiodic acid HI is 10 ~ 40wt%.
The preparation method of described graphene paper, the atmosphere surrounding described in step (3) is: vacuum, argon gas or hydrogen; Wherein vacuum tightness is 30KPa ~ 0.1Mpa, and argon pressure is 30KPa ~ 1Mpa, and hydrogen pressure is 30KPa ~ 1Mpa.
The preparation method of described graphene paper, in step (3), the temperature of described hot pressing environment is 100 DEG C ~ 900 DEG C, and pressure is 1 ~ 10Mpa.
The preparation method of described graphene paper, in step (3), described clamp time is: 5 ~ 60min.
The graphene paper prepared of described method above, can separately or with other material (as macromolecular material, metallic substance etc.) be hot pressed into stratified composite as structure-function integrated material for electromagnetic shielding, electrode materials, highly to dispel the heat, corrosion-resistant, high-abrasive material etc.
Compared with prior art, tool of the present invention has the following advantages:
Method relatively now, low temperature high yield in enormous quantities can prepare the graphene powder of high conductivity, reduce cost, laying a good foundation for preparing High-performance graphene paper; Relatively present preparation method, the present invention adopts compression molding to prepare thickness and the controlled graphene paper of area, lay a good foundation, expanded the range of application of grapheme material, and operating process is simple for preparing structure-function integrated material, can industrialization; Relatively present preparation method, method of the present invention prepare graphene film mechanical property and electroconductibility than existing graphene film or paper all high.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
Under condition of ice bath, 3.0g graphite is joined in the vitriol oil of 60ml, violent stirring 30min, further by 12gKMnO
4join in above-mentioned mixed solution, violent stirring 30min.Above-mentioned mixed solution is transferred in 30 DEG C of water-baths, slowly add 18gNaNO
3, stir 60min; Under agitation, 140ml deionized water is joined continuously in above-mentioned mixed solution, then transferred in the oil bath of 90 DEG C of temperature, stir the 30min time; Dropwise add 18mlH again
2o
2, continue reaction 60min and make solution become glassy yellow from dark-brown; Under stirring environment, in above-mentioned glassy yellow graphene oxide solution, drip 20ml acetic acid (concentration is 30wt%) go back original reagent, at 60 DEG C of temperature, react 1h, obtain black powder.By centrifugal for above-mentioned powder, with water cleaning, repeats 2 times, then centrifugal again, with ethanol purge 1 time, drying 24 hours at 40 DEG C.Above-mentioned dried graphene powder is joined in mould, mold pressing 5min at 1.0Mpa pressure, ar gas environment (30Kpa) and 100 DEG C of temperature.Can prepare 10 μm of thick graphene paper by aforesaid method, electric conductivity is 150S/cm, and mechanical stretch intensity is 120Mpa, and Young's modulus is 45Gpa.
Embodiment 2
Under condition of ice bath, 3.0g graphite is joined in the vitriol oil of 60ml, violent stirring 30min, further by 12gKMnO
4join in above-mentioned mixed solution, violent stirring 30min.Above-mentioned mixed solution is transferred in 30 DEG C of water-baths, slowly add 18gNaNO
3, stir 60min; Under agitation, 140ml deionized water is joined continuously in above-mentioned mixed solution, then transferred in the oil bath of 90 DEG C of temperature, stir the 30min time; Dropwise add 18mlH again
2o
2, continue reaction 60min and make solution become glassy yellow from dark-brown; Under stirring environment, in above-mentioned glassy yellow graphene oxide solution, drip 20ml acetic acid (concentration is 30wt%) go back original reagent, at 60 DEG C of temperature, react 1h, obtain black powder.By centrifugal for above-mentioned powder, with water cleaning, repeats 2 times, then centrifugal again, with ethanol purge 1 time, drying 24 hours at 40 DEG C.Above-mentioned dried graphene powder is joined in mould, mold pressing 20min at 10Mpa pressure, ar gas environment (1.0Mpa) and 900 DEG C of temperature.Can prepare 75 μm of thick graphene paper by aforesaid method, electric conductivity is 690S/cm, and mechanical stretch intensity is 430Mpa, and Young's modulus is 75Gpa.
Embodiment 3
Under condition of ice bath, 3.0g graphite is joined in the vitriol oil of 60ml, violent stirring 30min, further by 12gKMnO
4join in above-mentioned mixed solution, violent stirring 30min.Above-mentioned mixed solution is transferred in 30 DEG C of water-baths, slowly add 18gNaNO
3, stir 60min; Under agitation, 140ml deionized water is joined continuously in above-mentioned mixed solution, then transferred in the oil bath of 90 DEG C of temperature, stir the 30min time; Dropwise add 18mlH again
2o
2, continue reaction 60min and make solution become glassy yellow from dark-brown; Under stirring environment, in above-mentioned glassy yellow graphene oxide solution, drip 20ml acetic acid (concentration is 30wt%) go back original reagent, at 60 DEG C of temperature, react 1h, obtain black powder.By centrifugal for above-mentioned powder, with water cleaning, repeats 2 times, then centrifugal again, with ethanol purge 1 time, drying 24 hours at 40 DEG C.Above-mentioned dried graphene powder is joined in mould, mold pressing 5min at 10Mpa pressure, hydrogen environment (1.0Mpa) and 100 DEG C of temperature.Can prepare 74 μm of thick graphene paper by aforesaid method, electric conductivity is 750S/cm, and mechanical stretch intensity is 550Mpa, and Young's modulus is 69Gpa.
Embodiment 4
Under condition of ice bath, 3.0g graphite is joined in the vitriol oil of 60ml, violent stirring 30min, further by 12gKMnO
4join in above-mentioned mixed solution, violent stirring 30min.Above-mentioned mixed solution is transferred in 30 DEG C of water-baths, slowly add 18gNaNO
3, stir 60min; Under agitation, 140ml deionized water is joined continuously in above-mentioned mixed solution, then transferred in the oil bath of 90 DEG C of temperature, stir the 30min time; Dropwise add 18mlH again
2o
2, continue reaction 60min and make solution become glassy yellow from dark-brown; Under stirring environment, in above-mentioned glassy yellow graphene oxide solution, drip 20ml acetic acid (concentration is 30wt%) go back original reagent, at 60 DEG C of temperature, react 1h, obtain black powder.By centrifugal for above-mentioned powder, with water cleaning, repeats 2 times, then centrifugal again, with ethanol purge 1 time, drying 24 hours at 40 DEG C.The graphene powder of 0.5g after above-mentioned drying is joined in mould, mold pressing 20min at 10Mpa pressure, hydrogen environment (1.0Mpa) and 900 DEG C of temperature.Can prepare 73 μm of thick graphene paper by aforesaid method, electric conductivity is 880S/cm, and mechanical stretch intensity is 690Mpa, and Young's modulus is 85Gpa.
Embodiment 5
Under condition of ice bath, 3.0g graphite is joined in the vitriol oil of 60ml, violent stirring 30min, further by 12gKMnO
4join in above-mentioned mixed solution, violent stirring 30min.Above-mentioned mixed solution is transferred in 30 DEG C of water-baths, slowly add 18gNaNO
3, stir 60min; Under agitation, 140ml deionized water is joined continuously in above-mentioned mixed solution, then transferred in the oil bath of 90 DEG C of temperature, stir the 30min time; Dropwise add 18mlH again
2o
2, continue reaction 60min and make solution become glassy yellow from dark-brown; Under stirring environment, in above-mentioned glassy yellow graphene oxide solution, drip 20ml acetic acid (concentration is 30wt%) go back original reagent, at 60 DEG C of temperature, react 1h, obtain black powder.By centrifugal for above-mentioned powder, with water cleaning, repeats 2 times, then centrifugal again, with ethanol purge 1 time, drying 24 hours at 40 DEG C.The graphene powder of 1g after above-mentioned drying is joined in mould, mold pressing 10min at 10Mpa pressure, hydrogen environment (0.5Mpa) and 500 DEG C of temperature.Can prepare the thick graphene paper of 4mm by aforesaid method, electric conductivity is 750S/cm, and mechanical stretch intensity is 550Mpa, and Young's modulus is 75Gpa.
Claims (8)
1. a preparation method for High-performance graphene paper, is characterized in that, its step is as follows:
(1) under condition of ice bath, 1.0g ~ 5g graphite is joined in the vitriol oil of 50 ~ 200ml, violent stirring 20 ~ 40min; Further by 8g ~ 20g KMnO
4join in above-mentioned mixed solution, violent stirring 20 ~ 40min; Above-mentioned mixed solution is transferred in 10 DEG C ~ 30 DEG C water-baths, slowly add 10g ~ 30g NaNO
3, stir 40min ~ 80min; Under agitation, 100ml ~ 300ml deionized water is joined continuously in above-mentioned mixed solution, then transferred in the oil bath of 60 DEG C ~ 100 DEG C of temperature, stir 20 ~ 40min time; Dropwise add 10ml ~ 40ml H again
2o
2, continue reaction 40min ~ 80min until solution becomes glassy yellow from dark-brown;
(2) under stirring environment, in above-mentioned glassy yellow graphene oxide solution, drip hydrazine hydrate and the PVP mixing solutions of 10ml ~ 40ml, at 40 DEG C ~ 80 DEG C temperature, react 30min ~ 2h; In above-mentioned solution, drip 20ml also original reagent further, continue reaction 20 ~ 60min, the black powder be precipitated; By centrifugal for above-mentioned powder, with water cleaning, repeats 2 times, then centrifugal again, with ethanol purge 1 time, to be less than at 50 DEG C drying 24 hours;
(3) join in mould by a certain amount of above-mentioned dried graphene powder, under the hot pressing environment that certain pressure, certain atmosphere surrounding and temperature are formed, mold pressing certain hour, can prepare thickness and the controlled graphene paper of area.
2. the preparation method of graphene paper as claimed in claim 1, it is characterized in that, described in step (2), the concentration of the PVP aqueous solution is 1 ~ 15wt%.
3. the preparation method of graphene paper as claimed in claim 1, it is characterized in that, going back original reagent described in step (2) is acetic acid or hydroiodic acid HI.
4. the preparation method of graphene paper as claimed in claim 3, is characterized in that, the concentration of aqueous solution going back original reagent described in step (2): acetic acid is 10 ~ 30wt%, hydroiodic acid HI is 10 ~ 40wt%.
5. the preparation method of graphene paper as claimed in claim 1, it is characterized in that, the atmosphere surrounding described in step (3) is: vacuum, argon gas or hydrogen; Wherein vacuum tightness is 30KPa ~ 0.1Mpa, and argon pressure is 30KPa ~ 1Mpa, and hydrogen pressure is 30KPa ~ 1Mpa.
6. the preparation method of graphene paper as claimed in claim 1, it is characterized in that, in step (3), the temperature of described hot pressing environment is 100 DEG C ~ 900 DEG C, and pressure is 1 ~ 10Mpa.
7. the preparation method of graphene paper as claimed in claim 1, it is characterized in that, in step (3), described clamp time is: 5 ~ 60min.
8. graphene paper method described in claim 1 to 7 prepared separately or be hot pressed into macromolecular material, metallic substance that stratified composite is used for electromagnetic shielding, electrode materials as structure-function integrated material, highly dispels the heat, corrosion-resistant, high-abrasive material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310101522.6A CN103145124B (en) | 2013-03-27 | 2013-03-27 | High-performance graphene paper and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310101522.6A CN103145124B (en) | 2013-03-27 | 2013-03-27 | High-performance graphene paper and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103145124A CN103145124A (en) | 2013-06-12 |
| CN103145124B true CN103145124B (en) | 2015-01-14 |
Family
ID=48543513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310101522.6A Expired - Fee Related CN103145124B (en) | 2013-03-27 | 2013-03-27 | High-performance graphene paper and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103145124B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787315B (en) * | 2013-12-26 | 2016-03-09 | 中山大学 | A kind of preparation method of graphene platelet |
| CN104231295B (en) * | 2014-09-10 | 2017-03-01 | 中国科学院金属研究所 | A kind of preparation method of Graphene prepreg |
| CN104401987B (en) * | 2014-11-26 | 2016-10-12 | 东华大学 | A kind of preparation method of porous graphene elastic foam |
| CN104743551B (en) * | 2015-03-27 | 2017-03-01 | 上海应用技术学院 | A kind of preparation method of redox graphene heat conduction thin film |
| CN108859300B (en) * | 2018-06-14 | 2020-09-29 | 沈阳航空航天大学 | High-sensitivity graphene flexible strain sensor and preparation method thereof |
| CN108910865A (en) * | 2018-07-21 | 2018-11-30 | 哈尔滨工业大学 | A method of preparing graphene/graphene nanobelt mixed film |
| CN110395716A (en) * | 2019-07-26 | 2019-11-01 | 中国电子科技集团公司第三十三研究所 | A kind of preparation method of the microwave defense material based on graphene |
| CN113555229B (en) * | 2020-04-26 | 2023-04-21 | 中天超容科技有限公司 | Graphene paper current collector, preparation method and supercapacitor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009049375A1 (en) * | 2007-10-19 | 2009-04-23 | University Of Wollongong | Process for the preparation of graphene |
| CN102070142A (en) * | 2010-12-14 | 2011-05-25 | 四川大学 | Method for preparing graphene by chemical oxidation reduction |
| CN102583340A (en) * | 2012-01-20 | 2012-07-18 | 中国科学院上海硅酸盐研究所 | High-conductivity graphene material with low-temperature gas-phase reduction and preparation method thereof |
-
2013
- 2013-03-27 CN CN201310101522.6A patent/CN103145124B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009049375A1 (en) * | 2007-10-19 | 2009-04-23 | University Of Wollongong | Process for the preparation of graphene |
| CN102070142A (en) * | 2010-12-14 | 2011-05-25 | 四川大学 | Method for preparing graphene by chemical oxidation reduction |
| CN102583340A (en) * | 2012-01-20 | 2012-07-18 | 中国科学院上海硅酸盐研究所 | High-conductivity graphene material with low-temperature gas-phase reduction and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 赵南等.两步还原法制备石墨烯薄膜.《材料导报B:研究篇》.2013,第27卷(第3期),8-11. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103145124A (en) | 2013-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103145124B (en) | High-performance graphene paper and preparation method thereof | |
| Deng et al. | Superelastic, ultralight, and conductive Ti3C2T x MXene/acidified carbon nanotube anisotropic aerogels for electromagnetic interference shielding | |
| Zhao et al. | Pressure-induced self-interlocked structures for expanded graphite composite papers achieving prominent EMI shielding effectiveness and outstanding thermal conductivities | |
| CN103483516B (en) | Preparation method of graphene oxide-boron-modified phenolic resin | |
| Xie et al. | NiMn hydroxides supported on porous Ni/graphene films as electrically and thermally conductive electrodes for supercapacitors | |
| CN104973596A (en) | Hetero atom-doped hollow spherical grapheme composite material, and preparation method and applications thereof | |
| Wu et al. | Design of interconnected carbon fiber thermal management composites with effective EMI shielding activity | |
| CN102769124B (en) | Graphene-supported octahedral nickel oxide composite material and preparation method thereof | |
| CN108217627B (en) | Preparation method of independent self-supporting graphene carbon tube composite membrane | |
| CN104973591A (en) | High-quality graphene and preparation method thereof | |
| CN103723708A (en) | Preparation method of organic single-layer graphene solution | |
| CN103407991A (en) | Preparation method of nickel/nickel oxide-decorated nitrogen-doped graphene material | |
| CN103951916A (en) | RGO (Reduced Graphene oxide)/ferric oxide-filled polyvinylidene fluoride composite wave-absorbing material and preparation method thereof | |
| Liu et al. | Hierarchical structural evolution of Zn2GeO4 in binary solvent and its effect on Li-ion storage performance | |
| CN112280540A (en) | Preparation method of high-thermal-conductivity graphene-metal particle composite material | |
| Song et al. | Carbon fibers embedded with aligned magnetic particles for efficient electromagnetic energy absorption and conversion | |
| Li et al. | Copper-coated reduced graphene oxide fiber mesh-polymer composite films for electromagnetic interference shielding | |
| CN107697905A (en) | A kind of preparation method of three-dimensional nitrogen-doped graphene aeroge | |
| CN113416334A (en) | Hydroxyethyl cellulose/boron nitride nano composite film and preparation method thereof | |
| CN112357910A (en) | Preparation method of oriented graphene composite macroscopic body | |
| Yan et al. | MXene/CNTs/aramid aerogels for electromagnetic interference shielding and joule heating | |
| CN108611511B (en) | A kind of three-dimensional intercommunication CNTs/Cu composite material and preparation method | |
| Yan et al. | Ultra-wideband electromagnetic interference shielding effectiveness composite with elevated thermal conductivity | |
| Pan et al. | Enhanced thermal conductivity with ultralow filler loading via constructing branch-type heat transfer network | |
| CN103723712A (en) | Preparation method of single-layer graphene dimethylformamide solution |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150114 Termination date: 20190327 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |