CN103787321B - A kind of self-supporting grapheme material and preparation method thereof - Google Patents
A kind of self-supporting grapheme material and preparation method thereof Download PDFInfo
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- CN103787321B CN103787321B CN201410029985.0A CN201410029985A CN103787321B CN 103787321 B CN103787321 B CN 103787321B CN 201410029985 A CN201410029985 A CN 201410029985A CN 103787321 B CN103787321 B CN 103787321B
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Abstract
The present invention discloses a kind of self-supporting grapheme material and preparation method thereof, and this grapheme material forms three-dimensional self supporting structure by the Graphene grown on matrix, and its preparation method is by starch thermal treatment, washing, filtration drying.Mixed with alkali by dried product, under anaerobic after sintering processes, washing, dries, obtains self-supporting Graphene again.Compare traditional preparation methods and raw materials used, above-mentioned self-supporting graphene preparation method and raw materials used, have easy to operate, technological process is easy, and cost is low, and the Graphene prepared has the advantages such as self supporting structure, is particularly suitable for large-scale commercial production.
Description
Technical field
The invention belongs to new material technology field, particularly relate to a kind of self-supporting grapheme material and preparation method thereof.
Background technology
Graphene is a kind of novel material by the individual layer sheet structure of charcoal atomic building.Be a kind of by charcoal atom with sp
2hybridized orbital composition hexangle type is the flat film of honeycomb lattice, only has the two-dimensional material of a charcoal atomic thickness.Because of the calorifics of its uniqueness, mechanics, electric property and receiving much concern.Be deep into practical application from theoretical investigation for the research of Graphene in recent years and studied, it has been employed for the electrode materials of ultracapacitor and lithium ion battery.
At present, graphene preparation method can be summarized as: micromechanics partition method, chemical Vapor deposition process, SiC epitaxial growth method and graphene oxide reduction method etc.Micromechanics partition method is with adhesive tape or other means directional separation highly oriented pyrolytic graphites; the method technique simply but to yield poorly and uncontrollable; industrialization and large-scale production requirement can not be met; and it is more difficult to find single-layer graphene from the thick-layer of sheet; also there is a little glue stain in sample simultaneously; surface clearness is not high, limit its Graphene preparation in application.Chemical Vapor deposition process refers to that reactive material issues biochemical reaction at gaseous condition, produces the solid matrix surface that solid matter is deposited on heating, and then the Technology of obtained solid material.But the shortcoming of the method is that the cost preparing Graphene is higher relative to other preparation methods.SiC epitaxial growth method preparation condition is harsh, need high temperature and ultrahigh vacuum(HHV), and SiC material is expensive.The single-layer graphene prepared of graphene oxide reduction method is unstable, be easily polymerized.
Therefore find that a kind of technological process is simple, in enormous quantities, the preparation method of the Graphene of low cost, good stability is a problem in urgent need to solve.
Summary of the invention
Object of the present invention is exactly for the deficiencies in the prior art, a kind of self-supporting grapheme material and preparation method thereof is provided, mainly solve that complex technical process in existing graphene preparation method, cost are high, the problem of poor stability, simple, the economic environmental protection of low raw-material cost, technological process of this preparation method, is applicable to large-scale industrialized production and application.
Concrete technical scheme of the present invention there is provided a kind of self-supporting grapheme material and preparation method thereof, and this grapheme material forms three-dimensional self supporting structure by the Graphene grown on matrix.
The preparation method of a kind of self-supporting grapheme material of the present invention, specifically comprises following steps:
(1) by after starch drying, heat-treat under anaerobic, described thermal treatment temp is 400 ~ 500 DEG C, washs after thermal treatment, filters, dry;
(2) be after step (1) dried product is mixed with alkali, the mass ratio of described alkali and step (1) product is 1:20 ~ 20:1, sintering processes under anaerobic, described sintering processes temperature is 800 ~ 1200 DEG C, described sintering processes soaking time is 0.5 ~ 6h cooling, and washing, filters, drying, namely obtains self-supporting grapheme material.
In above-mentioned steps (1) and step (2), described being cooled to naturally cools to 10 ~ 30 DEG C; Described washing is with hydrochloric acid and distilled water wash respectively; Described filtration adopts suction filtration, and the number of times of described filtration is 5 ~ 6 times; Described drying is dry under condition of normal pressure.
In described step (1), described starch is tapioca (flour), W-Gum, cationic starch, oxidative crosslinked starch, Zulkovsky starch, graft starch.
Described starch is tapioca (flour), Zulkovsky starch.
In described step (2), described alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide, copper hydroxide, nickel hydroxide, ironic hydroxide, calcium hydroxide, hydrated barta.
Described alkali is sodium hydroxide, nickel hydroxide.
In described step (2), described alkali and the mass ratio of step (1) product are 1:1,1.5:1.
In described step (2), described sintering processes temperature is 800 ~ 850 DEG C.
In described step (2), described sintering processes soaking time is 0.5-1h.
The self-supporting grapheme material that the preparation method of described self-supporting grapheme material prepares.
On the basis meeting this area general knowledge, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material are all commercially.
Beneficial effect of the present invention is: Graphene prepared by the present invention has self supporting structure and cost is low, technique is simple, convenient and swift, is applicable to extensive commercial application.
Accompanying drawing explanation
Fig. 1 is Graphene preparation flow figure of the present invention;
Fig. 2 is that the self-supporting Graphene SEM prepared by the embodiment of the present invention 6 schemes;
Fig. 3 is the Raman spectrum of the self-supporting graphite Raman prepared by the embodiment of the present invention 6.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further elaborated, but is not limitation of the invention.
Embodiment 1:
The lower 350 DEG C of thermal treatments of tube furnace protection of inert gas put into by the tapioca (flour) of 5g by step (1); at 350 DEG C of insulation 2 ~ 4h; after reacting completely, filtered respectively by mixture with hydrochloric acid and water washing 5 ~ 6 times, the black powder obtained is dry in convection oven.
Dried for 1g product and 1g sodium hydroxide are added suitable quantity of water and mix by step (2); in the lower 800 DEG C of sintering of protection of inert gas/bury, insulation 0.5h process; room temperature is naturally cooled to after terminating; gained black powder is used respectively hydrochloric acid and water washing 3 ~ 5, in air dry oven, namely drying is obtained self-supporting grapheme material.
Embodiment 2
The W-Gum of 5g is put into the lower 400 DEG C of thermal treatments of tube furnace protection of inert gas by step (1); at 400 DEG C of insulation 2 ~ 4h; after reacting completely, filtered respectively by mixture with hydrochloric acid and water washing 5 ~ 6 times, the black powder obtained is dry in convection oven.
Dried for 1g product and 1g sodium hydroxide are added suitable quantity of water and mix by step (2); blanketing with inert gas/bury lower 900 DEG C of sintering, insulation 0.5h process; room temperature is naturally cooled to after terminating; gained black powder is used respectively hydrochloric acid and water washing 3 ~ 5, in air dry oven, namely drying is obtained self-supporting grapheme material.
Embodiment 3
The cationic starch of 5g is put into the lower 450 DEG C of thermal treatments of tube furnace protection of inert gas by step (1); at 450 DEG C of insulation 2 ~ 4h; after reacting completely, mixture is filtered with hydrochloric acid and water washing 5 ~ 6 times respectively, obtain black powder is dry in convection oven.
Dried for 1g product and 2g potassium hydroxide are added suitable quantity of water and mix by step (2); blanketing with inert gas/bury lower 850 DEG C of sintering, insulation 0.5h process; room temperature is naturally cooled to after terminating; the black powder of gained is used respectively hydrochloric acid and water washing 3 ~ 5, in air dry oven, drying obtains self-supporting grapheme material.
Embodiment 4
The oxidative crosslinked starch of 5g is put into the lower 500 DEG C of thermal treatments of tube furnace protection of inert gas by step (1); at 500 DEG C of insulation 2 ~ 4h; after reacting completely, filtered respectively by mixture with hydrochloric acid and water washing 5 ~ 6 times, the black powder obtained is dry in convection oven.
Dried for 1g product and 5g ironic hydroxide are added suitable quantity of water and mix by step (2); blanketing with inert gas/bury lower 950 DEG C of sintering, insulation 0.5h process; room temperature is naturally cooled to after terminating; gained black powder is used respectively hydrochloric acid and water washing 3 ~ 5, in air dry oven, drying obtains self-supporting grapheme material.
Embodiment 5
The lower 550 DEG C of thermal treatments of tube furnace protection of inert gas put into by the Zulkovsky starch of 5g by step (1); at 550 DEG C of insulation 2 ~ 4h; after reacting completely, filtered respectively by mixture with hydrochloric acid and water washing 5 ~ 6 times, the black powder obtained is dry in convection oven.
Dried for 1g product and 10g nickel hydroxide are added suitable quantity of water and mix by step (2); blanketing with inert gas/bury lower 980 DEG C of sintering, insulation 0.5h process; room temperature is naturally cooled to after terminating; gained black powder is used respectively hydrochloric acid and water washing 3 ~ 5, in air dry oven, drying obtains self-supporting grapheme material.
Embodiment 6
The W-Gum of 5g is put into the lower 600 DEG C of thermal treatments of tube furnace protection of inert gas by step (1); at 600 DEG C of insulation 2 ~ 4h; after reacting completely, filtered respectively by mixture with hydrochloric acid and water washing 5 ~ 6 times, the black powder obtained is dry in convection oven.
Dried for 1g product and 1g sodium hydroxide are added suitable quantity of water and mix by step (2); blanketing with inert gas/bury lower 1100 DEG C of sintering, insulation 0.5h process; room temperature is naturally cooled to after terminating; gained black powder is used respectively hydrochloric acid and water washing 3 ~ 5, in air dry oven, drying obtains self-supporting grapheme material.
Fig. 2 is the Electronic Speculum figure of self-supporting Graphene, and as can be seen from Figure 2, the Graphene that the present invention obtains is a kind of Graphene with self supporting structure.
Fig. 3 is the Raman spectrogram of self-supporting Graphene.Raman spectrum changes for graphite electronic structure strong response, is therefore often used as the effective means characterizing graphite and Graphene.In figure 3,1580cm
-1place G is with peak to correspond to the E of graphite
2gpattern, it and sp
2the vibration of charcoal atom is relevant.1347cm
-1the D band at place corresponds to the defect of graphite, 2690cm
-1place can be observed 2D band.Although independent D band and 2D band can not be used for the sign of the Graphene number of plies, are also the strong evidences of graphite linings electronic structure change.I
d/ I
g< 1 illustrates the greying of the charcoal after sintering processes, and what therefore prepare is a kind of Graphene of self supporting structure.
Claims (9)
1. a preparation method for self-supporting grapheme material, is characterized in that comprising the steps:
(1) by after starch drying, heat-treat under anaerobic, described thermal treatment temp is 400 ~ 500 DEG C, washs after thermal treatment, filters, dry;
(2) be after step (1) dried product is mixed with alkali, the mass ratio of described alkali and step (1) product is 1:20 ~ 20:1, sintering processes under anaerobic, described sintering processes temperature is 800 ~ 1200 DEG C, described sintering processes soaking time is 0.5 ~ 6h cooling, and washing, filters, drying, namely obtains self-supporting grapheme material;
In above-mentioned steps (1) and step (2), described being cooled to naturally cools to 10 ~ 30 DEG C; Described washing is with hydrochloric acid and distilled water wash respectively; Described filtration adopts suction filtration, and the number of times of described filtration is 5 ~ 6 times; Described drying is dry under condition of normal pressure.
2. the preparation method of self-supporting grapheme material according to claim 1, is characterized in that, in described step (1), described starch is tapioca (flour), W-Gum, cationic starch, oxidative crosslinked starch, Zulkovsky starch, graft starch.
3. the preparation method of self-supporting grapheme material according to claim 2, is characterized in that described starch is tapioca (flour), Zulkovsky starch.
4. the preparation method of self-supporting grapheme material according to claim 1, is characterized in that, in described step (2), described alkali is sodium hydroxide, potassium hydroxide, copper hydroxide, nickel hydroxide, ironic hydroxide, calcium hydroxide, hydrated barta.
5. the preparation method of self-supporting grapheme material according to claim 4, is characterized in that described alkali is sodium hydroxide, nickel hydroxide.
6. the preparation method of self-supporting grapheme material according to claim 1, is characterized in that in described step (2), and described alkali and the mass ratio of step (1) product are 1:1,1.5:1.
7. the preparation method of self-supporting grapheme material according to claim 1, is characterized in that, in described step (2), described sintering processes temperature is 800 ~ 850 DEG C.
8. the preparation method of self-supporting grapheme material according to claim 1, is characterized in that, in described step (2), described sintering processes soaking time is 0.5-1h.
9. the self-supporting grapheme material prepared of the preparation method of self-supporting grapheme material according to claim 1.
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| CN107673330A (en) * | 2017-10-31 | 2018-02-09 | 曾功昶 | A kind of method for preparing discarded object mangosteen shell graphene |
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| CN104355596B (en) * | 2014-10-17 | 2016-04-06 | 安徽永旭照明科技有限公司 | A kind of LED seat composition containing graphene microchip |
| CN105776171A (en) * | 2014-12-26 | 2016-07-20 | 广西师范大学 | Three-dimensional net structure carbon nanosheet material and preparation method thereof |
| CN106365152A (en) * | 2016-08-31 | 2017-02-01 | 南通绿业中试技术研究院有限公司 | Preparation method of graphene nanosheet |
| CN107381547A (en) * | 2017-07-27 | 2017-11-24 | 华南理工大学 | A kind of method for preparing grapheme material using frangipanis for raw material |
| CN107352529A (en) * | 2017-08-14 | 2017-11-17 | 华南理工大学 | A kind of method for preparing grapheme material using discarded object banana skin for raw material |
| CN107892291A (en) * | 2017-10-10 | 2018-04-10 | 华南理工大学 | A kind of method that grapheme material is prepared using discarded object coconut husk as raw material |
| CN115520861A (en) * | 2022-09-27 | 2022-12-27 | 福建师范大学 | Method for rapidly synthesizing graphite by utilizing multi-physical-field coupling effect and application |
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| CN101289183A (en) * | 2008-06-04 | 2008-10-22 | 天津大学 | Method for preparing starch based active carbon microballoons with high specific surface area |
| CN101525132A (en) * | 2009-04-15 | 2009-09-09 | 广西师范大学 | Active carbon for super capacitor and a preparation method thereof |
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| CN102544459A (en) * | 2012-01-09 | 2012-07-04 | 上海交通大学 | Method for preparing graphene-coated carbon microsphere material by coating graphene oxide on carbon microsphere |
| CN103265017A (en) * | 2013-05-17 | 2013-08-28 | 山西大学 | Preparation method of flexible self-supported paper graphene membrane and composite membrane thereof |
| CN103342348A (en) * | 2013-06-14 | 2013-10-09 | 中国石油大学(华东) | Preparation method for graphene/carbon microsphere composite |
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