CN104528708A - Preparation method of large-area few-layer graphene and dispersion solution thereof - Google Patents
Preparation method of large-area few-layer graphene and dispersion solution thereof Download PDFInfo
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- CN104528708A CN104528708A CN201510036320.7A CN201510036320A CN104528708A CN 104528708 A CN104528708 A CN 104528708A CN 201510036320 A CN201510036320 A CN 201510036320A CN 104528708 A CN104528708 A CN 104528708A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000006185 dispersion Substances 0.000 title claims abstract description 21
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 38
- 239000010439 graphite Substances 0.000 claims abstract description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000013543 active substance Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- -1 sodium alkyl benzene Chemical class 0.000 claims description 6
- 238000006396 nitration reaction Methods 0.000 claims description 5
- 239000011260 aqueous acid Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229940077388 benzenesulfonate Drugs 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 2
- 238000004299 exfoliation Methods 0.000 abstract 1
- 229960002163 hydrogen peroxide Drugs 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 238000004062 sedimentation Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 238000001507 sample dispersion Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Abstract
The invention belongs to the technical field of preparation of graphene materials, and particularly relates to a preparation method of large-area few-layer graphene and a dispersion solution thereof. The preparation method comprises the following steps: uniformly mixing natural crystalline flake graphite and mixed acid composed of concentrated nitric acid and concentrated sulfuric acid in a reactor, adding oxydol, reacting while stirring, then filtering, washing with water, and drying to obtain layered graphite; immersing the layered graphite in a volatile acid water solution, and sequentially filtering, washing with water and drying to obtain acidified layered graphite; and adding the acidified layered graphite into solvent containing surfactant, and performing ultrasonic exfoliation to obtain the graphene dispersion solution. The preparation method is simple in preparation process and convenient to operate; and the prepared graphene and graphene dispersion solution are superior in quality. The preparation method is wide in application range, environment-friendly, energy-saving and suitable for large-scale production.
Description
Technical field:
The invention belongs to grapheme material preparing technical field, particularly the preparation method of the few layer graphene of a kind of big area and dispersion liquid thereof.
Background technology:
Graphene (Graphene) be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the flat film of honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.It has very excellent performance, and such as its specific surface area is up to 2630m
2.g
-1, sign mobility is up to 200000cm
2.v
-1.s
-1, Young's modulus is nearly to 1.0TPa, and thermal conduction constant is 5000W.m
-1.K
-1, optical transmittance is up to 97.7%, and a little characteristics of Graphene make this type material be subject to extensive concern.
At present, the preparation method of Graphene mainly contains mechanically peel method, chemical Vapor deposition process, epitaxial growth method and chemistry redox method etc., these methods have its relative merits: mechanically peel method is due to the limitation of stripping means, and it is not suitable for heavy industrialization and prepares Graphene; Chemical Vapor deposition process and epitaxial growth method method owing to having complex process, condition is harsh, productive rate is low, high in cost of production shortcoming, limits its large-scale industrial production at Graphene and application; Although oxidation reduction process is prepare the comparatively common method of Graphene on a large scale at present, traditional Hummer method energy consumption is higher, easily to environment, and the Graphene defect obtained is many, easily assemble, the graphene dispersing solution poor stability of formation, Graphene size is less.Therefore the preparation method designing the few layer graphene of a kind of big area and dispersion liquid thereof is needed.
Summary of the invention:
The object of the invention is to the shortcoming overcoming prior art existence, seek to design the preparation method that the few layer graphene of a kind of big area and dispersion liquid thereof are provided, the Graphene area obtained is large, defect is few, the number of plies is few, the graphene dispersing solution obtained is uniformly dispersed, and good stability is with a wide range of applications.
In order to achieve the above object, specifically comprise the following steps when the present invention prepares big area few layer graphene dispersion liquid:
(1) by natural flake graphite and weight percent concentration be in the reactor 65% concentrated nitric acid and weight percent concentration be 98% the nitration mixture that forms of the vitriol oil mix, then adding weight percent concentration is 30% hydrogen peroxide, filter after 35 degrees Celsius of lower stirring reaction 1h, and be washed to pH=7, dry 8-12h at 60 c, obtain exfoliated graphite, wherein natural flake graphite: the nitration mixture of concentrated nitric acid and the vitriol oil: hydrogen peroxide=1g:5-10ml:1-2ml, the volume ratio of concentrated nitric acid and the vitriol oil is 1:1-3;
(2) exfoliated graphite being immersed in pH value is in the volatile aqueous acid of 1-3, filters, is washed to pH=7, at 60 c dry 8-12h, obtains the exfoliated graphite of acidifying;
(3) exfoliated graphite of acidifying is joined ultrasonic stripping in the solvent containing tensio-active agent and obtain graphene dispersing solution; Wherein the amount ratio of exfoliated graphite and solvent is 1g:100-200ml; The amount ratio of exfoliated graphite and tensio-active agent is 1g:0.5-2g; Ultrasonic power is 500w, and ultrasonic time is 30min-90min.
The present invention is first by graphene dispersing solution centrifugal 20min-40min under 6000rpm-8000rpm, then vacuum-drying 24h at 60 c, prepares graphene powder.
Reactor of the present invention is there-necked flask or four-hole boiling flask.
The sheet footpath size of natural flake graphite of the present invention is 150-300 μm, by realizing the regulation and control to Graphene Product size to the selection of natural flake graphite sheet footpath size.
Volatile acid of the present invention is one or more of hydrochloric acid, acetic acid or oxalic acid, exfoliated graphite is immersed in volatile aqueous acid, volatile acid is adsorbed onto between the lamella of exfoliated graphite, is conducive to graphite and peels off into Graphene.
Tensio-active agent of the present invention comprises the one in sodium alkyl benzene sulfonate, sodium alkyl sulfate, alkyl sodium sulfonate and sodium soap; Solvent be water, methyl alcohol, ethanol or tetrahydrofuran (THF).
The present invention compared with prior art, replace solid intercalator by hydrogen peroxide and prepare exfoliated graphite, then exfoliated graphite is immersed in volatile aqueous acid, Graphene is prepared in ultrasonic stripping in containing the solvent of tensio-active agent, and the Graphene splitting obtained is high, the number of plies few (1-5 layer), area large (mostly being 20-100 μm), due to not through redox processes, in reaction process, there is no NO, NO
2deng the generation of toxic gas, and the Graphene defect obtained is little; The graphene dispersing solution concentration obtained is high, reaches 5mg/ml, is uniformly dispersed, and highly stable under the existence of tensio-active agent, the not sedimentations of standing some months; Its preparation technology is simple, and easy to operate, Graphene and the graphene dispersing solution quality of preparation are good, and applied range, environmental protection and energy saving, are suitable for scale operation.
Accompanying drawing illustrates:
Fig. 1 is graphene dispersing solution picture prepared by the embodiment of the present invention, and wherein a, b, c are respectively graphene dispersing solution prepared by embodiment 1,2,3.
Fig. 2 is the XRD figure of the natural graphite of the embodiment of the present invention 1 use and the Graphene of preparation.
Fig. 3 is the TEM figure of Graphene prepared by the embodiment of the present invention 1.
Fig. 4 is the SEM figure of Graphene prepared by the embodiment of the present invention 1.
Fig. 5 is the AFM figure of Graphene prepared by the embodiment of the present invention 1.
Embodiment:
Also by reference to the accompanying drawings the present invention is described in further detail below by embodiment.
Embodiment 1:
The present embodiment specifically comprises the following steps when preparing the few layer graphene dispersion liquid of big area:
(1) to get 5g purity be 99% footpath size is that the natural flake graphite 5g of 150 μm mixes with the nitration mixture that 30ml concentrated nitric acid and the vitriol oil form, and wherein the volume of concentrated nitric acid is 10ml, and the volume of the vitriol oil is 20ml; Then add 10ml hydrogen peroxide, filter, and be washed to pH=7 under 35 degree after stirring reaction 1h, dry 10h obtains exfoliated graphite at 60 c;
(2) join in aqueous hydrochloric acid by exfoliated graphite 2g, adjust ph is to 1, and carry out filtering, washing after soaking 5min, dry 12h at 60 c, obtains the exfoliated graphite of acidifying;
(3) exfoliated graphite of getting 1g acidifying joins in 200ml ethanol, adds 1g Sodium dodecylbenzene sulfonate simultaneously, and namely the ultrasonic 60min of 500w obtains Graphene alcohol dispersion liquid.
The present embodiment is by Graphene ethanolic soln centrifugal 30min under 6000rpm of preparation, and by the solid washing obtained, vacuum-drying 12h obtains Graphene at 60 c.
As shown in Figure 1a, whole sample dispersion very even, concentration can reach 5mg/ml to Graphene alcohol dispersion liquid prepared by the present embodiment, can keep not sedimentation in two months.
The XRD figure of the Graphene of the natural graphite that the present embodiment uses and preparation as shown in Figure 2, after delamination, natural graphite almost disappears at 26.5 degree of strongly sharp-pointed (002) characteristic peaks, and be the characteristic peak of the Graphene (002) at the small steamed bun shape of 26 degree of appearance one, illustrate that graphite is stripped into Graphene.
The Graphene TEM that the present embodiment 1 obtains schemes as shown in Figure 3, and as can be seen from Figure, obtained graphene film area is comparatively large, and evenly overall, have the fold morphology of typical graphite alkene, the number of plies is few, is 1-3 layer.
The SEM figure of the Graphene that the present embodiment obtains as shown in Figure 4, can observe the typical fold pattern of Graphene.
As shown in Figure 5, as can be seen from Figure, the graphene sheet layer area of preparation is large, and size can reach 50 μm, and sample is even, and thickness is less than 1nm for the AFM figure of the Graphene that the present embodiment obtains, and illustrates that the Graphene of preparation is for few layer graphene, 1-3 layer.
Embodiment 2:
The same with embodiment 1 of other step of the present embodiment, only use water as solvent in the preparation process of step (3) graphene dispersing solution, as shown in Figure 1 b, sample dispersion is comparatively even for the graphene aqueous solution obtained, concentration can reach 2mg/ml, can keep not sedimentation in two weeks.
Embodiment 3:
The same with embodiment 1 of other step of the present embodiment, in the preparation process of step (3) graphene dispersing solution, only use tetrahydrofuran (THF) as solvent, the tetrahydrofuran (THF) dispersion liquid of the Graphene obtained as illustrated in figure 1 c, sample dispersion is very even, concentration can reach 2mg/ml, keeps a not sedimentation in month.
Embodiment 4:
The same with embodiment 1 of other step of the present embodiment, in the preparation process of step (3) graphene dispersing solution, only use sodium alkyl sulfate, alkyl sodium sulfonate and sodium soap as tensio-active agent, the Graphene obtained is similar to the result in embodiment 1 with graphene dispersing solution.
Embodiment 5:
The same with embodiment 1 of other step of the present embodiment, only immerse in step (2) exfoliated graphite in the step of volatile acid and adopt oxalic acid, adjust ph is 3, soak time is 2min, it is less that the Graphene obtained compares sheet footpath compared with the Graphene in embodiment 1, for 10-30 μm, and the number of plies is more, is 3-5 layer.
Embodiment 6:
The same with embodiment 1 of other step of the present embodiment, only immerse in step (2) exfoliated graphite in the step of volatile acid and adopt acetic acid, adjust ph is 2, and soak time is 3min, and the Graphene obtained is similar to the result in embodiment 1 with graphene dispersing solution.
Embodiment 7:
The same with embodiment 1 of other step of the present embodiment, only in the preparation process of step (3) graphene dispersing solution, do not add tensio-active agent, the Graphene alcohol dispersion liquid that result obtains is dispersed general, sedimentation in two weeks.
Embodiment 8:
The same with embodiment 2 of other step of the present embodiment, only in the preparation process of graphene aqueous solution, do not add tensio-active agent, the graphene aqueous solution dispersiveness that result obtains is poor, sedimentation in a week.
Embodiment 9:
The same with embodiment 3 of other step of the present embodiment, only in the preparation process of graphene dispersing solution, do not add tensio-active agent, the Graphene tetrahydrofuran (THF) dispersion liquid that result obtains is dispersed general, sedimentation in a week.
Claims (6)
1. a preparation method for the few layer graphene dispersion liquid of big area, is characterized in that the concrete steps prepared are:
(1) by natural flake graphite and weight percent concentration be in the reactor 65% concentrated nitric acid and weight percent concentration be 98% the nitration mixture that forms of the vitriol oil mix, then adding weight percent concentration is 30% hydrogen peroxide, filter after 35 degrees Celsius of lower stirring reaction 1h, and be washed to pH=7, dry 8-12h at 60 c, obtain exfoliated graphite, wherein natural flake graphite: the nitration mixture of concentrated nitric acid and the vitriol oil: hydrogen peroxide=1g:5-10ml:1-2ml, the volume ratio of concentrated nitric acid and the vitriol oil is 1:1-3;
(2) exfoliated graphite being immersed in pH value is in the volatile aqueous acid of 1-3, filters, is washed to pH=7, at 60 c dry 8-12h, obtains the exfoliated graphite of acidifying;
(3) exfoliated graphite of acidifying is joined ultrasonic stripping in the solvent containing tensio-active agent and obtain graphene dispersing solution; Wherein the amount ratio of exfoliated graphite and solvent is 1g:100-200ml; The amount ratio of exfoliated graphite and tensio-active agent is 1g:0.5-2g; Ultrasonic power is 500w, and ultrasonic time is 30min-90min.
2. big area lacks the preparation method of layer graphene dispersion liquid according to claim 1, it is characterized in that described reactor is there-necked flask or four-hole boiling flask.
3. big area lacks the preparation method of layer graphene dispersion liquid according to claim 1, it is characterized in that the sheet footpath size of described natural flake graphite is 150-300 μm.
4. big area lacks the preparation method of layer graphene dispersion liquid according to claim 1, it is characterized in that the acid of described volatile is hydrochloric acid, acetic acid or oxalic acid one or more.
5. big area lacks the preparation method of layer graphene dispersion liquid according to claim 1, it is characterized in that described tensio-active agent comprises the one in sodium alkyl benzene sulfonate, sodium alkyl sulfate, alkyl sodium sulfonate and sodium soap; Solvent be water, methyl alcohol, ethanol or tetrahydrofuran (THF).
6. the method adopting the few layer graphene dispersion liquid of big area as claimed in claim 5 to prepare Graphene, it is characterized in that graphene dispersing solution centrifugal 20min-40min under 6000rpm-8000rpm, vacuum-drying 24h at 60 c again, prepares graphene powder.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273114A (en) * | 2015-11-23 | 2016-01-27 | 复旦大学 | Method for preparing low oxidation degree graphene-modified polymethyl methacrylate (PMMA) composite material |
| CN107201071A (en) * | 2016-05-20 | 2017-09-26 | 南京长江涂料有限公司 | A kind of graphene sheet Conductive mica oil tank static electricity conductive anticorrosive paint and preparation method thereof |
| CN107573557A (en) * | 2017-10-12 | 2018-01-12 | 沈阳航空航天大学 | The method that solution blended process prepares graphene/elastomer nanocomposites |
| CN108889035A (en) * | 2018-08-03 | 2018-11-27 | 太仓曌信金属制品有限公司 | A kind of efficient anti-ultraviolet anti-static air filtration cotton |
| CN113582168A (en) * | 2020-04-30 | 2021-11-02 | 北京超思电子技术有限责任公司 | Graphene preparation method based on mixed inorganic acid solvent |
| WO2022180564A1 (en) | 2021-02-25 | 2022-09-01 | Politechnika Warszawska | A method for producing flaked graphene by intercalation and exfoliation of graphite |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103910354A (en) * | 2014-03-25 | 2014-07-09 | 复旦大学 | Method for preparing graphene through large-scale aqueous phase |
-
2015
- 2015-01-23 CN CN201510036320.7A patent/CN104528708A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910354A (en) * | 2014-03-25 | 2014-07-09 | 复旦大学 | Method for preparing graphene through large-scale aqueous phase |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273114A (en) * | 2015-11-23 | 2016-01-27 | 复旦大学 | Method for preparing low oxidation degree graphene-modified polymethyl methacrylate (PMMA) composite material |
| CN105273114B (en) * | 2015-11-23 | 2018-10-16 | 复旦大学 | A kind of preparation method of suboxides degree graphene modified poly (methyl methacrylate) composite material |
| CN107201071A (en) * | 2016-05-20 | 2017-09-26 | 南京长江涂料有限公司 | A kind of graphene sheet Conductive mica oil tank static electricity conductive anticorrosive paint and preparation method thereof |
| CN107573557A (en) * | 2017-10-12 | 2018-01-12 | 沈阳航空航天大学 | The method that solution blended process prepares graphene/elastomer nanocomposites |
| CN107573557B (en) * | 2017-10-12 | 2019-10-01 | 沈阳航空航天大学 | Solution blended process prepares graphene/elastomer nanocomposites method |
| CN108889035A (en) * | 2018-08-03 | 2018-11-27 | 太仓曌信金属制品有限公司 | A kind of efficient anti-ultraviolet anti-static air filtration cotton |
| CN113582168A (en) * | 2020-04-30 | 2021-11-02 | 北京超思电子技术有限责任公司 | Graphene preparation method based on mixed inorganic acid solvent |
| WO2022180564A1 (en) | 2021-02-25 | 2022-09-01 | Politechnika Warszawska | A method for producing flaked graphene by intercalation and exfoliation of graphite |
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