CN104229787A - Method for increasing yield of graphene prepared by supercritical fluid through pretreatment of natural graphite - Google Patents
Method for increasing yield of graphene prepared by supercritical fluid through pretreatment of natural graphite Download PDFInfo
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Abstract
The invention relates to a method for increasing the yield of graphene prepared by a supercritical fluid through pretreatment of natural graphite. The method comprises the steps as follows: natural graphite powder and acid are added into a container and stirred uniformly; an additive is added, and the mixture is cooled to obtain low-temperature graphite slurry; the low-temperature graphite slurry is sprayed to a high-pressure reaction kettle containing supercritical fluid media for supercritical treatment; and then a material after the supercritical treatment is rapidly sprayed into a normal-pressure production material tank and is filtered, separated and dried to obtain the graphene product. Compared with the prior art, the low-temperature natural graphite slurry pretreated by the acid is taken as feedstock; compared with the normal-temperature natural graphite serving as feedstock, the yield of graphene is increased by about 2-5 times through the supercritical fluid stripping process; and not only is the yield of graphene increased, but also the electrical property and the thermal property of graphene are further maintained.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, especially relate to method natural graphite pre-treatment being improved to preparing graphene by using supercritical fluid productive rate.
Background technology
Due to the special performance of Graphene, be thus with a wide range of applications in a lot of fields.In order to realize the commercial applications of Graphene, the most critical issue to obtain a large amount of high-quality graphenes.At present, many methods how preparing Graphene have been there is, as mechanically peel method, chemical reduction method etc.The Graphene obtained by mechanically peel method has excellent electrical property, but productive rate is very low; Oxidation reduction process can realize Graphene large-scale production, but the electrical property of the Graphene obtained is not too desirable.Supercutical fluid has excellent surface wettability ability, low surface tension, high diffusivity coefficient, low-viscosity coefficient, and these characteristics facilitate supercutical fluid intercalation and peel off graphite, prepare Graphene.Supercutical fluid is peeled off natural graphite and is prepared Graphene process, and be that a pure physics comes off process, do not introduce other impurity, therefore, the Graphene obtained has excellent electrical property and thermal characteristics.But the productive rate of Graphene is not very high.The present invention proposes the raw material peeled off as supercutical fluid by faint for the acid low temperature natural graphite slurry processed, and prepares Graphene.This invention substantially increases the productive rate that Graphene prepared by supercutical fluid stripping natural graphite, and meanwhile, Graphene has very high electrical property.
Application number be 201210001582.6 Chinese patent disclose supercritical co and peel off and prepare the method for big scale Graphene, employing supercritical CO
2for stripper, tensio-active agent is dispersion agent, and Graphite Powder 99 and dispersion agent are placed in autoclave, then pass into CO
2circulate under postcritical state, reduction of blood pressure in high-speed is to normal pressure afterwards, repeat said process, making material experience repeatedly boosting and pressure reduction, by controlling boosting and the step-down number of times control Graphene number of plies, namely preparing big scale Graphene, but the productive rate that the method finally obtains product is relatively low, this is also that the present invention needs emphatically technical solution problem.
Summary of the invention
Object of the present invention is exactly prepare to overcome supercutical fluid stripping natural graphite the problem that in Graphene method, productive rate is undesirable, propose using acid in advance the faint low temperature natural graphite slurry processed as the charging of autoclave, prepare Graphene, substantially increase the productive rate of Graphene, meanwhile, the intrinsic property of Graphene does not also suffer damage.
Object of the present invention can be achieved through the following technical solutions:
Natural graphite pre-treatment is improved to the method for preparing graphene by using supercritical fluid productive rate, adopts following steps:
(1) natural graphite powder and acid to be joined in container and to stir;
(2) filter or be separated unnecessary acid, then in material, add additive and stir;
(3) above-mentioned material to be transferred in low-temperature (low temperature) vessel and to lower the temperature, obtaining the graphite slurry of low temperature;
(4) low temperature graphite slurry is injected to fast fills in the autoclave of supercritical fluid media;
(5) control the temperature and pressure of material in autoclave, and material is stopped in autoclave carry out first supercritical processing;
(6) material after first supercritical processing being injected to fast normal pressure produces in batch can;
(7) filter, be separated the material also drying of producing in batch can, obtain Graphene product.
In step (1), the weight ratio of natural graphite powder and acid is 1: 10 ~ 10: 1, the acid adopted is the hydrochloric acid that concentration is greater than the sulfuric acid of 70wt%, concentration is greater than 65wt% nitric acid or concentration are greater than 37wt%, natural graphite powder and sour stir process 5 ~ 60 minutes.
Additive described in step (2) is ethylene glycol or ethanol, and addition is 0.1 ~ 5% of Graphite Powder 99 weight.
In step (3), graphite slurry is cooled to-30 ~ 0 DEG C.
Supercritical fluid media described in step (4) includes but not limited to carbonic acid gas, ethanol, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, 1-dodecyl-2-Pyrrolidone, dimethyl formamide, dromisol, Virahol, N-octyl group-2-Pyrrolidone, acetone, tetrahydrofuran (THF), hexanaphthene or methyl alcohol.
As preferred embodiment, supercritical fluid media can adopt ethanol, CO
2, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF) or N-Methyl pyrrolidone.
In step (5) mesohigh reactor, the temperature and pressure of material is close to the critical temperature of supercritical fluid media and pressure, and wherein temperature is 30 ~ 390 DEG C, and pressure is 2 ~ 40MPa, and material residence time in autoclave is 15 ~ 120 minutes.
Wherein, when adopting carbonic acid gas as supercritical fluid media, in autoclave, the temperature of material is 35 DEG C, pressure is 7.5Mpa, residence time of material is 60 minutes; When adopting ethanol as supercritical fluid media, temperature of charge is 245 DEG C, pressure is 6.5Mpa, the residence time is 50 minutes; When N,N-DIMETHYLACETAMIDE is supercritical fluid media, temperature of charge is 270 DEG C, pressure is 6Mpa, the residence time is 40 minutes.
Adopt vacuum-drying in step (7), drying temperature is 35 ~ 100 DEG C, and time of drying is 1 ~ 12 hour.
Compared with prior art, the innovative content of patent of the present invention is: (1) is by improving the productive rate of follow-up stripping product to the pre-treatment of graphite raw material; (2) method to raw materials pretreatment is disclosed, by the concrete technology of acid treatment and subzero treatment; (3) principle why pre-treatment can improve productive rate is illustrated, specific as follows:
The raw material that the low temperature natural graphite slurry that the present invention utilizes acid to anticipate is peeled off as supercutical fluid, because the temperature of graphite is lower, when being injected in hot environment fast, strong thermal shocking can be subject to, generation microexplosion is split by graphite granule interlayer, and this just provides favourable breach for follow-up molecule intercalation.Secondly, natural graphite is after the faint process of peracid, adhere to the polarity oxygen-containing functional group (hydroxyl, carboxyl) of some amount on the surface, in supercutical fluid intercalation process, polarity oxygen-containing functional group can adsorb the organic solvent polar molecule of supercritical state by bipolarity interattraction, when intercalated molecule is stacked in the porthole of the graphite layers of micro rupture, facilitate supercutical fluid molecule and complete intercalation process, substantially increase Graphene productive rate.Finally, because polarity oxygen-containing functional group can be reduced in supercritical fluid environment (High Temperature High Pressure), the intrinsic property of Graphene is not therefore affected.The low temperature natural graphite slurry of acid being anticipated is as charging, and with normal temperature natural graphite as compared with charging, by supercutical fluid stripping process, the productive rate of Graphene improves and is about 2 ~ 5 times.The present invention not only increases the productive rate of Graphene, and maintains electrical property and thermal characteristics that Graphene has.
Accompanying drawing explanation
Fig. 1 is the AFM figure of the Graphene that the embodiment of the present invention obtains.
Embodiment
Embodiments of the invention are described in detail as follows, and the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention are not limited to following embodiment.
Natural graphite pre-treatment is improved to the method for preparing graphene by using supercritical fluid productive rate, adopts following steps:
(1) natural graphite powder and acid to be joined in container and to stir, the weight ratio of natural graphite powder wherein and acid is 1: 10 ~ 10: 1, the acid adopted is the hydrochloric acid that concentration is greater than the sulfuric acid of 70wt%, concentration is greater than 65wt% nitric acid or concentration are greater than 37wt%, natural graphite powder and sour stir process 5 ~ 60 minutes;
(2) filter or be separated unnecessary acid, in material, then add ethylene glycol or ethanol additive and stir, addition is 0.1 ~ 5% of Graphite Powder 99 weight;
(3) above-mentioned material to be transferred in low-temperature (low temperature) vessel and to be cooled to-30 ~ 0 DEG C, obtaining the graphite slurry of low temperature;
(4) be injected to fast by low temperature graphite slurry and fill in the autoclave of supercritical fluid media, operable supercritical fluid media includes carbonic acid gas, ethanol, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, 1-dodecyl-2-Pyrrolidone, dimethyl formamide, dromisol, Virahol, N-octyl group-2-Pyrrolidone, acetone, tetrahydrofuran (THF), hexanaphthene or methyl alcohol;
(5) temperature and pressure controlling material in autoclave is close to the critical temperature of supercritical fluid media and pressure, and material is stopped in autoclave carry out first supercritical processing, such as, when adopting carbonic acid gas as supercritical fluid media, in autoclave, the temperature of material is 35 DEG C, pressure is 7.5Mpa, residence time of material is 60 minutes; When adopting ethanol as supercritical fluid media, temperature of charge is 245 DEG C, pressure is 6.5Mpa, the residence time is 50 minutes; When N,N-DIMETHYLACETAMIDE is supercritical fluid media, temperature of charge is 270 DEG C, pressure is 6Mpa, the residence time is 40 minutes;
(6) material after first supercritical processing being injected to fast normal pressure produces in batch can;
(7) filter, be separated and produce material in batch can and vacuum-drying, drying temperature is 35 ~ 100 DEG C, and time of drying is 1 ~ 12 hour, obtains Graphene product.
Below be described in detail.
Embodiment 1
Weight ratio by 10: 1 by natural graphite powder and 95% the vitriol oil, join in container, adopt ultrasonic agitation mode, stir after 20 minutes, unnecessary acid is filtered out.Add ethanol by 3% of Graphite Powder 99 weight, and stir.Material is transferred in low-temperature (low temperature) vessel, make material drop to-10 DEG C.Then being injected to fast by low-temperature material fills in the autoclave of Supercritical Ethanol, and the temperature of autoclave maintains 245 DEG C, and pressure is 6.5MPa.After material stops 60 minutes in autoclave, be injected to normal pressure fast and produce in batch can.By material filtering, separation, cleaning, drying and collection solid product.Solid product joins in fresh dimethyl formamide solution again, utilizes ul-trasonic irradiation to disperse, and the time is 120min, leave standstill 12 hours, adopt centrifugation mode (3000r/min, 10min) precipitation to be removed again, finally obtain graphene dispersing solution product.Shown by test analysis, material through autoclave cycle Graphene productive rate once reach ~ 23%, than the not pretreated productive rate of raw material improve nearly 2.6 times.
Embodiment 2
Weight ratio by 1: 2 by natural graphite powder and 80% concentrated hydrochloric acid, join in container, adopt mechanical stirring mode, stir after 40 minutes, unnecessary acid is filtered out.Add ethanol by 5% of Graphite Powder 99 weight, and stir.Material is transferred in low-temperature (low temperature) vessel, make material drop to-20 DEG C.Then be injected to fast by low-temperature material in the autoclave filling overcritical N-Methyl pyrrolidone, the temperature of autoclave maintains 445 DEG C, and pressure is 4.8MPa.After material stops 90 minutes in autoclave, be injected to normal pressure fast and produce in batch can.By material filtering, separation, cleaning, drying and collection solid product.Solid product joins in fresh dimethyl formamide solution again, utilizes ul-trasonic irradiation to disperse, and the time is 120min, leave standstill 12 hours, adopt centrifugation mode (3000r/min, 10min) precipitation to be removed again, finally obtain graphene dispersing solution product.Shown by test analysis, material through autoclave cycle Graphene productive rate once reach ~ 35%, than the not pretreated productive rate of raw material improve nearly 2.4 times.
Embodiment 3
Weight ratio by 1: 1 by natural graphite powder and 90% concentrated nitric acid, join in container, adopt mechanical stirring mode, stir after 50 minutes, unnecessary acid centrifuging is separated.Add ethylene glycol by 1% of Graphite Powder 99 weight, and stir.Material is transferred in low-temperature (low temperature) vessel, make material drop to-5 DEG C.Then be injected to fast by low-temperature material in the autoclave filling overcritical dimethyl formamide, the temperature of autoclave maintains 370 DEG C, and pressure is 6MPa.After material stops 120 minutes in autoclave, be injected to normal pressure fast and produce in batch can.By material filtering, separation, cleaning, drying and collection solid product.Solid product joins in fresh dimethyl formamide solution again, utilizes ul-trasonic irradiation to disperse, and the time is 120min, leave standstill 12 hours, adopt centrifugation mode (3000r/min, 10min) precipitation to be removed again, finally obtain graphene dispersing solution product.Shown by test analysis, material through autoclave cycle Graphene productive rate once reach ~ 46%, than the not pretreated productive rate of raw material improve nearly 3 times.Fig. 1 is the AFM figure of the graphene product that the present embodiment prepares, by pre-treatment disclosed by the invention, the stripping productive rate of Graphene can be improved, this is because: when low-temperature pulp is injected in hot environment fast, strong thermal shocking can be subject to, cause graphite granule interlayer generation microexplosion to split, be very easy to molecule intercalation.Secondly, after the faint process of acid, the polar functional group that graphite surface adheres to, is conducive to absorption intercalation polar molecule; When intercalated molecule is stacked in the porthole of the graphite layers of micro rupture, significantly promote intercalation speed, thus substantially increase Graphene productive rate.
Claims (10)
1. pair natural graphite pre-treatment improves the method for preparing graphene by using supercritical fluid productive rate, it is characterized in that, the method adopts following steps:
(1) natural graphite powder and acid to be joined in container and to stir;
(2) filter or be separated unnecessary acid, then in material, add additive and stir;
(3) above-mentioned material to be transferred in low-temperature (low temperature) vessel and to lower the temperature, obtaining the graphite slurry of low temperature;
(4) low temperature graphite slurry is injected to fast fills in the autoclave of supercritical fluid media;
(5) control the temperature and pressure of material in autoclave, and material is stopped in autoclave carry out first supercritical processing;
(6) material after first supercritical processing being injected to fast normal pressure produces in batch can;
(7) filter, be separated the material also drying of producing in batch can, obtain Graphene product.
2. method natural graphite pre-treatment being improved to preparing graphene by using supercritical fluid productive rate according to claim 1, is characterized in that, in step (1), the weight ratio of natural graphite powder and acid is 1: 10 ~ 10: 1.
3. method natural graphite pre-treatment being improved to preparing graphene by using supercritical fluid productive rate according to claim 1 and 2, it is characterized in that, the acid described in step (1) is the hydrochloric acid that concentration is greater than the sulfuric acid of 70wt%, concentration is greater than 65wt% nitric acid or concentration are greater than 37wt%.
4. method natural graphite pre-treatment being improved to preparing graphene by using supercritical fluid productive rate according to claim 1, is characterized in that, natural graphite powder and sour stir process 5 ~ 60 minutes in step (1).
5. method natural graphite pre-treatment being improved to preparing graphene by using supercritical fluid productive rate according to claim 1, it is characterized in that, the additive described in step (2) is ethylene glycol or ethanol, and addition is 0.1 ~ 5% of Graphite Powder 99 weight.
6. method natural graphite pre-treatment being improved to preparing graphene by using supercritical fluid productive rate according to claim 1, is characterized in that, in step (3), graphite slurry is cooled to-30 ~ 0 DEG C.
7. method natural graphite pre-treatment being improved to preparing graphene by using supercritical fluid productive rate according to claim 1, it is characterized in that, the supercritical fluid media described in step (4) includes but not limited to carbonic acid gas, ethanol, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE, 1-dodecyl-2-Pyrrolidone, dimethyl formamide, dromisol, Virahol, N-octyl group-2-Pyrrolidone, acetone, tetrahydrofuran (THF), hexanaphthene or methyl alcohol.
8. method natural graphite pre-treatment being improved to preparing graphene by using supercritical fluid productive rate according to claim 7, is characterized in that, described supercritical fluid media preferred alcohol, CO
2, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF) or N-Methyl pyrrolidone.
9. method natural graphite pre-treatment being improved to preparing graphene by using supercritical fluid productive rate according to claim 1, it is characterized in that, in step (5) mesohigh reactor, the temperature and pressure of material is close to the critical temperature of supercritical fluid media and pressure, wherein temperature is 30 ~ 390 DEG C, pressure is 2 ~ 40MPa, and material residence time in autoclave is 15 ~ 120 minutes.
10. method natural graphite pre-treatment being improved to preparing graphene by using supercritical fluid productive rate according to claim 1, is characterized in that, adopt vacuum-drying in step (7), drying temperature is 35 ~ 100 DEG C, and time of drying is 1 ~ 12 hour.
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| WO2017048524A1 (en) | 2015-09-17 | 2017-03-23 | Arisdyne Systems, Inc. | Method of forming graphene material by graphite exfoliation |
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| CN105129790A (en) * | 2015-10-10 | 2015-12-09 | 杭州海虹精细化工有限公司 | Novel method for preparing graphene oxide under supercritical water condition |
| CN105645391A (en) * | 2016-01-06 | 2016-06-08 | 大连理工大学 | Method for preparing graphene by stripping natural graphite powder in CO2 expanded liquid by introducing dislocation glide actions |
| CN107335253A (en) * | 2016-04-29 | 2017-11-10 | 北京化工大学常州先进材料研究院 | A kind of method that supercritical carbon dioxide prepares blocky graphite alkene porous material |
| CN107337465A (en) * | 2016-04-29 | 2017-11-10 | 北京化工大学常州先进材料研究院 | A kind of method that supercritical carbon dioxide prepares block CNT porous material |
| CN114590804A (en) * | 2022-01-26 | 2022-06-07 | 深圳市翔丰华科技股份有限公司 | Method for efficiently preparing doped graphene through supercritical fluid |
| CN117383549A (en) * | 2023-02-19 | 2024-01-12 | 烯源科技无锡有限公司 | Method for preparing low-defect nanoscale graphene by physical method |
| CN117383549B (en) * | 2023-02-19 | 2024-04-26 | 烯源科技无锡有限公司 | Method for preparing low-defect nanoscale graphene by physical method |
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