CN103112850A - Method for preparing high-quality graphene through catalytic oxidation multiple-intercalation - Google Patents
Method for preparing high-quality graphene through catalytic oxidation multiple-intercalation Download PDFInfo
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- CN103112850A CN103112850A CN2013100803693A CN201310080369A CN103112850A CN 103112850 A CN103112850 A CN 103112850A CN 2013100803693 A CN2013100803693 A CN 2013100803693A CN 201310080369 A CN201310080369 A CN 201310080369A CN 103112850 A CN103112850 A CN 103112850A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000009830 intercalation Methods 0.000 title claims abstract description 26
- 230000003647 oxidation Effects 0.000 title claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 title abstract 2
- 230000002687 intercalation Effects 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- 238000002203 pretreatment Methods 0.000 claims description 12
- 238000010907 mechanical stirring Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- 238000011946 reduction process Methods 0.000 claims description 5
- 239000000138 intercalating agent Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 238000011085 pressure filtration Methods 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002356 single layer Substances 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- -1 hydroxy free radical Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention relates to a method for preparing high-quality graphene through catalytic oxidation multiple-intercalation. The method comprises the following steps of: (1) pretreating; (2) carrying out intercalation peeling; (3) repeatedly carrying out the pretreating of the step (1) and the intercalation peeling of the step (2) on a product obtained in the step (2) to obtain a graphene product; and (4) washing the graphene product obtained in the step (3) and carrying out integrated filtration and drying on the graphene product obtained in the step (3); and (5) placing the dried product in a reduction protective atmosphere for deoxidation, thus obtaining the high-performance graphene. The method has the advantages of controlled reaction, high production efficiency, environmental friendliness, low energy consumption, high yield of single-layer graphene and few structure faults of graphene, and is simple and practicable in technology.
Description
Technical field
The present invention relates to a kind of catalyzed oxidation repeatedly intercalation prepare the method for high-quality graphene, belong to the Graphene preparation field.
Background technology
Since Graphene was found in 2004, it had caused the very big concern of scientific circles immediately as a kind of new carbon.Graphene has unique two-dimensional nanostructure, and its electric transmission speed is high, conductivity is superior, thermal conductivity is high, is the highest material of known physical strength and possesses the advantages such as the stable chemical performance light transmission is good.Graphene has application prospect very widely in fields such as lithium ion battery, ultracapacitor, functional composite material, sensor, biological medicine, transparent conductive film, microelectronic devices.
Up to the present, the preparation method of known Graphene has: 1) micromechanics stripping method.The method can only as fundamental research, can't be accomplished scale production; 2) Graphene epitaxial growth method.The method expensive limited its practical application; 3) chemical Vapor deposition process.The method can satisfy the requirement of large-scale production, but cost is higher, complex process; 4) oxidation reduction process.The method is by becoming graphite oxide with graphite oxidation, and graphite oxide is peeled off the generation graphene oxide, then prepares Graphene by chemistry or thermal reduction.The method has a distinct increment on preparative-scale, but excessive with acid amount in production process, environmental pollution is serious, and there is more defect and impurity in the low and Graphene product of reaction process and reaction product controllable degree, is difficult to obtain the highly purified product of high quality.
Summary of the invention
Technical problem to be solved by this invention is the technology of preparing present situation for present Graphene, provides a kind of reaction controlled, and production efficiency is high, and technological process is simple, environmental protection less energy-consumption and the high preparation method of Graphene quality.Products obtained therefrom single-layer graphene productive rate is high, and the Two-dimensional electron structural integrity has excellent chemical physics performance.
For realizing purpose of the present invention, technical scheme of the present invention is as follows:
A kind of catalyzed oxidation repeatedly intercalation prepares the method for high-quality graphene, and the method comprises the following steps:
(1) pre-treatment step: graphite is placed in by Fe
2+With H
2O
2In the mixing solutions that consists of, obtain the Graphitic pretreatment product by mechanical stirring or supersound process or uviolizing, then product is carried out filtration washing;
(2) intercalation strip step: will be placed in by the Graphitic pretreatment product that step (1) obtains intercalator solution and carry out simultaneously supersound process, washing obtains multi-layer graphene after filtration;
(3) with pre-treatment and the intercalation strip step of above-mentioned multi-layer graphene recirculation step (1) and (2), obtain the Graphene product;
(4) the Graphene product by step (3) gained washs and integrated filtration and drying;
(5) above-mentioned dried product is placed in reduction protection atmosphere and carries out deoxidation and reduction, namely obtain the high-performance Graphene.
In a preferred embodiment of the present invention, the Fe in described step (1)
2+With H
2O
2Mol ratio be 1:10-1:60, the pH value of mixing solutions is 1-5, the treatment time is 1-5h.
In a preferred embodiment of the present invention, the mechanical stirring speed in described step (1) is 100-3000rpm, and ultrasonic power is 100-5000W, and ultraviolet wavelength is 190-400nm.
In a preferred embodiment of the present invention, the intercalator in described step (2) is quaternary ammonium salt.
In a more preferred embodiment of the present invention, described quaternary ammonium salt is one or more the mixture in cetyl trimethylammonium bromide, Trimethyllaurylammonium bromide, ten alkyl trimethyl ammonium bromides, Tetrabutyl amonium bromide or tetraethylammonium bromide.
In a preferred embodiment of the present invention, intercalation in described step (2) is peeled off and supersound process is carried out in being aided with churned mechanically sonic oscillation system, and wherein, mechanical stirring speed is 100-3000rpm, ultrasonic power is 100-5000W, and the treatment time is 30-300min.
In a preferred embodiment of the present invention, it is 1-10 time that the circulation pre-treatment of described step (3) and intercalation are peeled off number of times.
In a preferred embodiment of the present invention, the filtration of described step (4) and dry by the drying integrated dewatering process realization of thermal air pressure filtration.
In a preferred embodiment of the present invention, the reduction protection atmosphere of described step (5) is that hydrogen and argon gas are according to the mixing of different ratios, wherein, the volume ratio of hydrogen and argon gas is 3:97-5:95, the flow that reduction protection atmosphere enters stove is 100-300CC/min, and the reduction heat-up rate is 5-40 ℃/min; High temperature deoxidation and reduction process temperature is controlled at 400-1000 ℃, and the control constant temperature time is 1-10h, then is cooled to room temperature with furnace temperature.
Compared with prior art, of the present invention having the following advantages:
(1) the present invention adopts controlled catalysed oxidation processes, utilizes H
2O
2The activity hydroxy free radical that produces is opened the graphite layers edge, reduces the destructiveness to conjugated backbone in graphite linings, effectively protects the integrity of Graphene crystalline structure;
(2) adopt the large size quaternary ammonium salt that graphite layers is inserted, effectively increase the graphite layers distance, be conducive to the follow-up of graphite and peel off;
(3) intercalation of graphite and liquid phase stripping process carry out in integrating device simultaneously, and both synergy can effectively improve manufacture efficient;
(4) filtration drying technique realizes on single equipment by the thermal air pressure filtration drying dehydration process, and it is remarkable that technological process has energy-saving effect, the high and solid recovery rate advantages of higher of operating efficiency.
Description of drawings
Fig. 1 is the atomic force microscope figure of the Graphene for preparing of embodiment 1.
Fig. 2 is the transmission electron microscope picture of the Graphene for preparing of embodiment 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of the Graphene for preparing of embodiment 1.
Fig. 4 is the atomic force microscope figure of the Graphene for preparing of embodiment 2.
Fig. 5 is the atomic force microscope figure of the Graphene for preparing of embodiment 3.
Embodiment
Below in conjunction with example, concrete enforcement of the present invention is described further, but enforcement of the present invention and protection domain are not limited to this.
Embodiment 1
(1) pre-treatment step: 5g graphite is placed in 25ml Fe
2+With H
2O
2Mixed aqueous solution in, Fe wherein
2+With H
2O
2Mol ratio is 1:40, and the pH value of solution is 3, and mechanical stirring speed is 500rpm and is aided with the UV-irradiation 3h that wavelength is 254nm, then the Graphitic pretreatment product carried out filtration washing;
(2) intercalation strip step: will be placed in by the 4.5g Graphitic pretreatment product that step (2) obtain 20ml cetyl trimethylammonium bromide aqueous solution intercalation and peel off, mechanical stirring speed is 300rpm, ultrasonic power is 1000W, treatment time 60min, and washing obtains multi-layer graphene after filtration;
(3) with the pre-treatment of above-mentioned multi-layer graphene recirculation and intercalation stripping process twice, (volume ratio of hydrogen and argon gas is 3:97 at last the product after washing, filtering and drying to be placed in high temperature reduction atmosphere; The flow that reduction protection atmosphere enters stove is 100CC/min, and the reduction heat-up rate is 40 ℃/min; High temperature deoxidation and reduction process temperature is controlled at 900 ℃, and the control constant temperature time is 1h) thermal reduction obtains Graphene.
Fig. 1-3 are respectively atomic force microscope figure, transmission electron microscope picture and the scanning electron microscope (SEM) photograph of the Graphene that this embodiment obtains.Can find out, the thickness of Graphene is below 1nm, and the size of Graphene is chosen electron diffraction and shown that the crystallinity of Graphene is good about 5 μ m.The specific conductivity of Graphene can reach 10 after tested
3S/cm.
(1) pre-treatment step: 5g graphite is placed in 25ml Fe
2+With H
2O
2Mixed aqueous solution in, wherein, Fe
2+With H
2O
2Mol ratio is 1:30, and the pH value of solution is 4, and mechanical stirring speed is 400rpm and is aided with the UV-irradiation 2h that wavelength is 254nm, then the Graphitic pretreatment product carried out filtration washing;
(2) intercalation strip step: will be placed in by the 4.3g Graphitic pretreatment product that step (2) obtain 20ml tetrabutyl phosphonium bromide aqueous ammonium intercalation and peel off, mechanical stirring speed is 400rpm, ultrasonic power is 1200W, treatment time 60min, and washing obtains multi-layer graphene after filtration;
(3) with the pre-treatment of above-mentioned multi-layer graphene recirculation and intercalation stripping process three times, (volume ratio of hydrogen and argon gas is 3:97 at last the product after washing, filtering and drying to be placed in high temperature reduction atmosphere; The flow that reduction protection atmosphere enters stove is 150CC/min, and the reduction heat-up rate is 60 ℃/min; High temperature deoxidation and reduction process temperature is controlled at 1000 ℃, and the control constant temperature time is 1.5h) thermal reduction obtains Graphene.
The atomic force microscope figure of the Graphene that Fig. 4 obtains for this embodiment.Can find out that the lamellar spacing of Graphene is at 3-7nm.The specific conductivity of Graphene can reach 800S/cm after tested.
Embodiment 3
(1) pre-treatment step: 5g graphite is placed in 25ml Fe
2+With H
2O
2Mixed aqueous solution in, wherein, Fe
2+With H
2O
2Mol ratio is 1:50, and the pH value of solution is 2, and ultrasonic power is 800W, and the treatment time is 3h.Then the Graphitic pretreatment product is carried out filtration washing;
(2) intercalation strip step: will be placed in by the 4.6g Graphitic pretreatment product that step (2) obtain 20ml tetraethylammonium bromide aqueous solution intercalation and peel off, mechanical stirring speed is 200rpm, ultrasonic power is 800W, treatment time 120min, and washing obtains multi-layer graphene after filtration;
(3) with the pre-treatment of above-mentioned multi-layer graphene recirculation and intercalation stripping process twice, (volume ratio of hydrogen and argon gas is 4:96 at last the product after washing, filtering and drying to be placed in high temperature reduction atmosphere; The flow that reduction protection atmosphere enters stove is 120CC/min, and the reduction heat-up rate is 60 ℃/min; High temperature deoxidation and reduction process temperature is controlled at 1000 ℃, and the control constant temperature time is 2h) thermal reduction obtains Graphene.
The atomic force microscope figure of the Graphene that Fig. 5 obtains for this embodiment.Can find out that the lamellar spacing of Graphene is in the 27nm left and right.The specific conductivity of Graphene can reach 650S/cm after tested.Those skilled in the art can make replacement or modification to content of the present invention according to content disclosed by the invention and the art technology of grasping; but these replacements or modification should not be considered as breaking away from design of the present invention, and these replacements or modification are all in the claimed interest field of the present invention.
Claims (9)
- A catalyzed oxidation repeatedly intercalation prepare the method for high-quality graphene, it is characterized in that, the method comprises the following steps:(1) pre-treatment step: graphite is placed in by Fe 2+With H 2O 2In the mixing solutions that consists of, obtain the Graphitic pretreatment product by mechanical stirring or supersound process or uviolizing, then product is carried out filtration washing;(2) intercalation strip step: will be placed in by the Graphitic pretreatment product that step (1) obtains intercalator solution and carry out simultaneously supersound process, washing obtains multi-layer graphene after filtration;(3) with pre-treatment and the intercalation strip step of above-mentioned multi-layer graphene recirculation step (1) and (2), obtain the Graphene product;(4) the Graphene product by step (3) gained washs and integrated filtration and drying;(5) above-mentioned dried product is placed in reduction protection atmosphere and carries out deoxidation and reduction, namely obtain the high-performance Graphene.
- 2. preparation method according to claim 1, is characterized in that, the Fe in described step (1) 2+With H 2O 2Mol ratio be 1:10-1:60, the pH value of mixing solutions is 1-5, the treatment time is 1-5h.
- 3. preparation method according to claim 1, is characterized in that, the mechanical stirring speed in described step (1) is 100-3000rpm, and ultrasonic power is 100-5000W, and ultraviolet wavelength is 190-400nm.
- 4. preparation method according to claim 1, is characterized in that, the intercalator in described step (2) is quaternary ammonium salt.
- 5. preparation method according to claim 4, it is characterized in that, described quaternary ammonium salt is one or more the mixture in cetyl trimethylammonium bromide, Trimethyllaurylammonium bromide, ten alkyl trimethyl ammonium bromides, Tetrabutyl amonium bromide or tetraethylammonium bromide.
- 6. preparation method according to claim 1, it is characterized in that, intercalation in described step (2) is peeled off and supersound process is carried out in being aided with churned mechanically sonic oscillation system, wherein, mechanical stirring speed is 100-3000rpm, ultrasonic power is 100-5000W, and the treatment time is 30-300min.
- 7. preparation method according to claim 1, is characterized in that, it is 1-10 time that the circulation pre-treatment of described step (3) and intercalation are peeled off number of times.
- 8. preparation method according to claim 1, is characterized in that, the filtration of described step (4) and dry by the drying integrated dewatering process realization of thermal air pressure filtration.
- 9. preparation method according to claim 1, it is characterized in that, the reduction protection atmosphere of described step (5) is that hydrogen and argon gas are according to the mixing of different ratios, wherein, the volume ratio of hydrogen and argon gas is 3:97-5:95, the flow that reduction protection atmosphere enters stove is 100-300CC/min, and the reduction heat-up rate is 5-40 ℃/min; High temperature deoxidation and reduction process temperature is controlled at 400-1000 ℃, and the control constant temperature time is 1-10h, then is cooled to room temperature with furnace temperature.
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| CN106672957A (en) * | 2016-07-18 | 2017-05-17 | 中国科学院兰州化学物理研究所 | Method for preparing graphene oxide according to Fenton oxidation method |
| CN106744911A (en) * | 2017-01-23 | 2017-05-31 | 宣城亨旺新材料有限公司 | The production method of graphene oxide |
| CN107285302A (en) * | 2017-08-17 | 2017-10-24 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of graphene |
| CN107601489A (en) * | 2017-10-30 | 2018-01-19 | 嘉兴烯成新材料有限公司 | A kind of preparation method of graphene oxide |
| CN107673340A (en) * | 2017-11-22 | 2018-02-09 | 肇庆中特能科技投资有限公司 | Graphene and preparation method thereof |
| CN110642241A (en) * | 2019-06-16 | 2020-01-03 | 嘉兴烯成新材料有限公司 | Preparation method of semiconductor carbon material |
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| CN107285302A (en) * | 2017-08-17 | 2017-10-24 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of graphene |
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| CN107601489A (en) * | 2017-10-30 | 2018-01-19 | 嘉兴烯成新材料有限公司 | A kind of preparation method of graphene oxide |
| CN107673340A (en) * | 2017-11-22 | 2018-02-09 | 肇庆中特能科技投资有限公司 | Graphene and preparation method thereof |
| CN110642241A (en) * | 2019-06-16 | 2020-01-03 | 嘉兴烯成新材料有限公司 | Preparation method of semiconductor carbon material |
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| CN103112850B (en) | 2015-02-18 |
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