CN105293477A - Preparation method for large lamellar graphene oxide - Google Patents
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Abstract
A preparation method for large lamellar graphene oxide comprises the following steps: (1) performing intercalation processing on natural flake graphite by using a mixed acid solution, so as to obtain intercalation graphite, and then performing heat treatment on the intercalation graphite; (2) performing oxidation reaction on the intercalation graphite subjected to heat treatment, so as to obtain graphene oxide; and (3) adding a solvent into graphene oxide, fully dissolving to prepare a graphene oxide solution, then adjusting the pH value of the graphene oxide solution to be less than 7, and finally settling large lamellar graphene oxide by employing a standing processing or centrifugation processing process and performing separation. According to the method, the natural flake graphite raw material is subjected to intercalation processing and heat treatment in advance, more contact area is provided for a strong acid and a strong oxidant in a subsequent oxidation reaction process, and thus oxidation efficiency is improved. When the large lamellar graphene oxide is separated, the complexing effect of the solvent and an oxygen-containing group on graphene oxide is improved, and the separation effect is substantial.
Description
Technical field
The present invention relates to grapheme material field, relate in particular to a kind of preparation method of large lamella graphene oxide.
Background technology
In carbon material family, the people such as Univ Manchester UK Geim have found a new star member in 2004, Graphene.Graphene, monolayer carbon atom is with sp
2the bi-dimensional cellular shape material of hydridization, has the long-pending (2630m of high theoretical surface
2g
-1), the specific conductivity (10 of superelevation
3to10
4sm
-1), outstanding mechanical property, high thermal conductivity and chemical stability, the investigation and application in chemistry, electronics and Materials science be always various countries scientist and scholar chase focus.
As everyone knows, the lamella size of Graphene has great effect to the character of Graphene and application.Such as, large lamella graphene oxide (being greater than 5 μm) can be applied in many aspects, as the conductive film in three-dimensional grapheme base net network, handkerchief polymer based composites and optoelectronic device, compare with the graphene oxide of little lamella, large lamella graphene oxide has less contact resistance, thus can prepare the film of high conductivity.And the lamella size of general redox graphene depends on its graphene oxide presoma lamella size.
At present, the method preparing Graphene mainly contains machinery/liquid phase stripping method, epitaxial growth method, chemical Vapor deposition process and oxidation reduction process.Plant preparation method with first three to compare, oxidation reduction process is considered to the most economical effective method being applicable to suitability for industrialized production.The existing method preparing graphene oxide mainly comprises Hummer ' s method, Brodie method and Standenmaier method, and wherein Hummer ' s method is the most conventional.
But the graphene oxide size that existing method obtains is less, and output is not high, and the size of product mixes completely, distribution-free rule.
Therefore, how to realize the size of controlled oxidization Graphene, and how to realize the graphene oxide of different size size to separate to obtain large-sized graphene oxide, become the key point realizing suitability for industrialized production Graphene.
Summary of the invention
It is simple that technical problem to be solved by this invention is to provide a kind of technique, and cost is low, and output is high, effectively can increase the preparation method of the large lamella graphene oxide of graphene oxide lamella.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme: a kind of preparation method of large lamella graphene oxide, comprises the following steps:
(1) with mixed acid solution, intercalation processing is carried out to natural flake graphite, obtain intercalated graphite, then intercalated graphite is heat-treated;
(2) carry out oxidizing reaction to through heat treated intercalated graphite, obtain graphene oxide;
(3) in graphene oxide, solvent is added, graphene oxide solution is made after abundant dissolving, then the pH value of graphene oxide solution is adjusted to < 7, finally adopts the method for standing process or centrifugal treating by the sedimentation of large lamella graphene oxide and separate.
Preferably, the carbon content of described natural flake graphite is 80-99.9%, and granularity is 80-500 orders.
Preferably, described mixed acid solution is the nitration mixture of the vitriol oil and concentrated nitric acid or the strong phosphoric acid ratio mixing gained of 1-10:1 by volume, and the mass ratio of described mixed acid solution and natural flake graphite is 10-100:1.
Preferably, the temperature of intercalation processing is room temperature, the time is 20-24h.
Preferably, heat treated temperature is 1000-1100 DEG C, the time is 12-17s.
Preferably, described solvent is the mixed solution of any one or two or more arbitrary volume ratio in deionized water, tetrahydrofuran (THF), dimethyl formamide.
Preferably, the concentration of described graphene oxide solution is 0.1-10mg/ml.
Preferably, the pH value dilute hydrochloric acid of described graphene oxide solution or dilute sodium carbonate solution are adjusted to 2 ~ 6.
Preferably, leave standstill the number of times of process more than once, the time of each process is 1 ~ 36h.
Preferably, the number of times of centrifugal treating is more than once, and the rotating speed of each process is 4000-10000rpm/min, and the time is 5-30min.
Compared with prior art, beneficial effect of the present invention is:
1. the present invention carries out intercalation processing and thermal treatment to natural flake graphite raw material in advance, can for strong acid and strong oxidizer provide more contact area in follow-up oxidation reaction process, thus can oxidation efficiency be improved, the lamella of the graphene oxide obtained is increased, and productive rate gets a promotion.
2. the present invention is when being separated large lamella graphene oxide, first make graphene oxide solution, there is the oxygen-containing functional groups such as carbonyl in graphene oxide lamella, electrostatic repulsion between graphene oxide lamella stops graphene oxide to be assembled in a solvent, along with the increase of graphene oxide lamella, the oxygen-containing functional groups such as carbonyl can reduce thereupon, and thus the graphene oxide of little lamella has higher solubleness than the graphene oxide of large lamella.Therefore, the graphene oxide of large lamella can deposit, and the graphene oxide of little lamella rests in supernatant liquor; The pH value of graphene oxide solution is adjusted to < 7 by the present invention in addition, under the condition of pH value < 7, the lamella of graphene oxide can not be destroyed, and the complexing action of the oxygen-containing functional group on solvent and graphene oxide is improved, and separating effect is remarkable.
3. low raw-material cost of the present invention, be easy to get, technique is simple, and easy to operate, favorable reproducibility, can carry out large-scale industrial production, have extraordinary application prospect.
4. the graphene oxide that obtains of the present invention, compares the graphene oxide obtained by existing preparation method, and its lamella increases multiple can up to 5-6 times.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of the large lamella graphene oxide that the embodiment of the present invention 1 obtains.
Fig. 2 is the scanning electron microscope diagram of the large lamella graphene oxide that the embodiment of the present invention 2 obtains.
Fig. 3 is the scanning electron microscope diagram of the large lamella graphene oxide that the embodiment of the present invention 3 obtains.
Fig. 4 is the scanning electron microscope diagram of the large lamella graphene oxide that the embodiment of the present invention 4 obtains.
Fig. 5 is the scanning electron microscope diagram of the large lamella graphene oxide that the embodiment of the present invention 5 obtains.
Embodiment
Below in conjunction with accompanying drawing, embodiment, the invention will be further described:
General description is carried out to the material used in the present invention's experiment and test method in this part.Although for realizing many materials that the object of the invention uses and working method is well known in the art, the present invention describes in detail as far as possible at this.It will be apparent to those skilled in the art that hereinafter, if not specified, material therefor of the present invention, equipment and working method are well known in the art.The massfraction of the vitriol oil used is below 98%, the massfraction of concentrated nitric acid be 69% and the massfraction of strong phosphoric acid be 85%.
Embodiment 1
A preparation method for large lamella graphene oxide, comprises the following steps:
(1) under room temperature, get that 2g carbon content is 99.9%, granularity is 500 order natural flake graphites, add 100g mixed acid solution, then intercalation processing 20h under agitation, filtered by 5 μm of millipore filtrations afterwards, drying is carried out to the precipitation of filtering gained, obtains intercalated graphite, finally by intercalated graphite thermal treatment 12s under 1100 DEG C of conditions;
Described mixed acid solution is the nitration mixture of the vitriol oil and the concentrated nitric acid ratio mixing gained of 5:1 by volume;
(2) to adopting Hummer ' s method to carry out oxidizing reaction through heat treated intercalated graphite, graphene oxide is obtained;
The concrete steps of Hummer ' s method are as follows: 0 DEG C, under agitation condition, the vitriol oil is added in heat treated intercalated graphite, mix, add SODIUMNITRATE again, mix, slowly potassium permanganate is added again in 50min, mix, then 40 DEG C, react 24h under agitation condition, afterwards the mixed solution of reaction gained is poured in frozen water, under agitation condition, slowly add hydrogen peroxide, finally leave standstill process 12h, again by the precipitate and separate of standing gained out, after dilute hydrochloric acid cleaning, graphene oxide is obtained;
The mass ratio of described intercalated graphite and the vitriol oil, SODIUMNITRATE, potassium permanganate and hydrogen peroxide is 1:23:0.5:3:3.8;
(3) in graphene oxide, solvent is added, the graphene oxide solution that concentration is 5mg/ml is made after abundant dissolving, then with dilute hydrochloric acid, the pH value of graphene oxide solution is adjusted to 2, finally leaves standstill process 36h and the sedimentation of large lamella graphene oxide is separated;
Described solvent is the mixed solution of deionized water and the tetrahydrofuran (THF) ratio mixing gained of 1:1 by volume.
The scanning electron microscope diagram of the large lamella graphene oxide that the present embodiment obtains is shown in Fig. 1, and the present embodiment finally obtains 1.8 grams, size range is at the large lamella graphene oxide of 15-25 μm.
And with identical natural flake graphite for raw material, only adopting above-mentioned Hummer ' s method to carry out oxidizing reaction, the quality of the graphene oxide obtained is 1.5 grams, size range is 1-5 μm.
Embodiment 2
A preparation method for large lamella graphene oxide, comprises the following steps:
(1) under room temperature, get that 2g carbon content is 80%, granularity is 80 order natural flake graphites, add 20g mixed acid solution, then intercalation processing 24h under agitation, filtered by 5 μm of millipore filtrations afterwards, drying is carried out to the precipitation of filtering gained, obtains intercalated graphite, finally by intercalated graphite thermal treatment 17s under 1000 DEG C of conditions;
Described mixed acid solution is the nitration mixture of the vitriol oil and the strong phosphoric acid ratio mixing gained of 1:1 by volume;
(2) to adopting Hummer ' s method to carry out oxidizing reaction through heat treated intercalated graphite, graphene oxide is obtained;
The concrete steps of Hummer ' s method are as follows: 5 DEG C, under agitation condition, the vitriol oil is added in heat treated intercalated graphite, mix, add SODIUMNITRATE again, mix, slowly potassium permanganate is added again in 40min, mix, then 60 DEG C, react 2h under agitation condition, afterwards the mixed solution of reaction gained is poured in frozen water, under agitation condition, slowly add hydrogen peroxide, finally leave standstill process 24h, again by the precipitate and separate of standing gained out, after dilute hydrochloric acid cleaning, graphene oxide is obtained;
The mass ratio of described intercalated graphite and the vitriol oil, SODIUMNITRATE, potassium permanganate and hydrogen peroxide is 1:23:0.5:3:3.8;
(3) in graphene oxide, solvent is added, the graphene oxide solution that concentration is 2mg/ml is made after abundant dissolving, then with dilute sodium carbonate solution, the pH value of graphene oxide solution is adjusted to 6, finally adopt the method for centrifugal treating (rotating speed is 10000rpm/min, and the time is 30min) by the sedimentation of large lamella graphene oxide and separate;
Described solvent be deionized water and dimethyl formamide by volume 3:1 ratio mixing gained mixed solution.
The scanning electron microscope diagram of the large lamella graphene oxide that the present embodiment obtains is shown in Fig. 2, and the present embodiment finally obtains 1.6 grams, size range is at the large lamella graphene oxide of 45-60 μm.
And with identical natural flake graphite for raw material, only adopting above-mentioned Hummer ' s method to carry out oxidizing reaction, the quality of the graphene oxide obtained is 0.9 gram, size range is 15-20 μm.
Embodiment 3
A preparation method for large lamella graphene oxide, comprises the following steps:
(1) under room temperature, get that 2g carbon content is 85%, granularity is 200 order natural flake graphites, add 70g mixed acid solution, then intercalation processing 21h under agitation, filtered by 5 μm of millipore filtrations afterwards, drying is carried out to the precipitation of filtering gained, obtains intercalated graphite, finally by intercalated graphite thermal treatment 16s under 1025 DEG C of conditions;
Described mixed acid solution is the nitration mixture of the vitriol oil and the concentrated nitric acid ratio mixing gained of 10:1 by volume;
(2) to adopting Hummer ' s method to carry out oxidizing reaction through heat treated intercalated graphite, graphene oxide is obtained;
The concrete steps of Hummer ' s method are as follows: 10 DEG C, under agitation condition, the vitriol oil is added in heat treated intercalated graphite, mix, add SODIUMNITRATE again, mix, slowly potassium permanganate is added again in 30min, mix, then 50 DEG C, react 12h under agitation condition, afterwards the mixed solution of reaction gained is poured in frozen water, under agitation condition, slowly add hydrogen peroxide, finally leave standstill process 6h, again by the precipitate and separate of standing gained out, after dilute hydrochloric acid cleaning, graphene oxide is obtained;
The mass ratio of described intercalated graphite and the vitriol oil, SODIUMNITRATE, potassium permanganate and hydrogen peroxide is 1:23:0.5:3:3.8;
(3) in graphene oxide, solvent is added, the graphene oxide solution that concentration is 10mg/ml is made after abundant dissolving, then with dilute hydrochloric acid, the pH value of graphene oxide solution is adjusted to 3, carry out first time standing process again, first time leaves standstill process 24h, then is left standstill the precipitate and separate of process gained first time out, the above process of repeating step (3) is carried out second time and is left standstill process, second time leaves standstill process 9h, is left standstill process the sedimentation of large lamella graphene oxide and separate by twice;
Described solvent is the mixed solution of tetrahydrofuran (THF) and the dimethyl formamide ratio mixing gained of 1:4 by volume.
The scanning electron microscope diagram of the large lamella graphene oxide that the present embodiment obtains is shown in Fig. 3, and the present embodiment finally obtains 1.7 grams, size range is at the large lamella graphene oxide of 35-45 μm.
And with identical natural flake graphite for raw material, only adopting above-mentioned Hummer ' s method to carry out oxidizing reaction, the quality of the graphene oxide obtained is 1.1 grams, size range is 7-12 μm.
Embodiment 4
A preparation method for large lamella graphene oxide, comprises the following steps:
(1) under room temperature, get that 2g carbon content is 90%, granularity is 300 order natural flake graphites, add 150g mixed acid solution, then intercalation processing 22h under agitation, filtered by 5 μm of millipore filtrations afterwards, drying is carried out to the precipitation of filtering gained, obtains intercalated graphite, finally by intercalated graphite thermal treatment 14s under 1050 DEG C of conditions;
Described mixed acid solution is the nitration mixture of the vitriol oil and the strong phosphoric acid ratio mixing gained of 8:1 by volume;
(2) adopt Standenmaier method to carry out oxidizing reaction to through heat treated intercalated graphite, obtain graphene oxide;
The concrete steps of Standenmaier method are as follows: 0 DEG C, under agitation condition, the vitriol oil, concentrated nitric acid is added in heat treated intercalated graphite, mix, in 50min, slowly add Potcrate again, mix, then 40 DEG C, react 24h under agitation condition, add a large amount of deionized water afterwards, leave standstill process 12h, then by the precipitate and separate of standing gained out, after dilute hydrochloric acid cleaning, obtain graphene oxide;
The mass ratio of described intercalated graphite and the vitriol oil, concentrated nitric acid and Potcrate is 1:15:8:11;
(3) in graphene oxide, solvent is added, the graphene oxide solution that concentration is 0.1mg/ml is made after abundant dissolving, then with dilute sodium carbonate solution, the pH value of graphene oxide solution is adjusted to 5, carry out first time centrifugal treating again, the rotating speed of centrifugal treating is 7000rpm/min for the first time, time is 15min, then by first time centrifugal treating gained precipitate and separate out, the above process of repeating step (3) carries out second time centrifugal treating, second time centrifugal treating, the rotating speed of second time centrifugal treating is 4000rpm/min, time is 5min, by two times centrifugal process, the sedimentation of large lamella graphene oxide is separated,
Described solvent is deionized water.
The scanning electron microscope diagram of the large lamella graphene oxide that the present embodiment obtains is shown in Fig. 4, and the present embodiment finally obtains 1.7 grams, size range is at the large lamella graphene oxide of 25-35 μm.
And with identical natural flake graphite for raw material, only adopting above-mentioned Standenmaier method to carry out oxidizing reaction, the quality of the graphene oxide obtained is 1.2 grams, size range is 7-13 μm.
Embodiment 5
A preparation method for large lamella graphene oxide, comprises the following steps:
(1) under room temperature, get that 2g carbon content is 95%, granularity is 400 order natural flake graphites, add 200g mixed acid solution, then intercalation processing 23h under agitation, filtered by 5 μm of millipore filtrations afterwards, drying is carried out to the precipitation of filtering gained, obtains intercalated graphite, finally by intercalated graphite thermal treatment 13s under 1075 DEG C of conditions;
Described mixed acid solution is the nitration mixture of the vitriol oil and the concentrated nitric acid ratio mixing gained of 3:1 by volume;
(2) adopt Brodie method to carry out oxidizing reaction to through heat treated intercalated graphite, obtain graphene oxide;
The concrete steps of Brodie method are as follows: 0 DEG C, under agitation condition, concentrated nitric acid is added in heat treated intercalated graphite, mix, in 50min, slowly add Potcrate again, mix, then 40 DEG C, react 24h under agitation condition, add a large amount of deionized water afterwards, leave standstill process 12h, then by the precipitate and separate of standing gained out, after dilute hydrochloric acid cleaning, obtain graphene oxide;
The mass ratio of described intercalated graphite and concentrated nitric acid, Potcrate is 1:30:3;
(3) in graphene oxide, solvent is added, the graphene oxide solution that concentration is 8mg/ml is made after abundant dissolving, then with dilute hydrochloric acid, the pH value of graphene oxide solution is adjusted to 4, carry out first time standing process again, first time leaves standstill process 18h, then is left standstill the precipitate and separate of process gained first time out, the above process of repeating step (3) is carried out second time and is left standstill process, second time leaves standstill process 1h, then second time is left standstill the precipitate and separate of process gained out, the above process of repeating step (3) carries out third time standing process, third time leaves standstill process 1h, left standstill by three times and process the sedimentation of large lamella graphene oxide and separate,
Described solvent is tetrahydrofuran (THF).
The scanning electron microscope diagram of the large lamella graphene oxide that the present embodiment obtains is shown in Fig. 5, and the present embodiment finally obtains 1.7 grams, size range is at the large lamella graphene oxide of 20-30 μm.
And with identical natural flake graphite for raw material, only adopting above-mentioned Brodie method to carry out oxidizing reaction, the quality of the graphene oxide obtained is 1.2 grams, size range is 5-11 μm.
In the present invention, deionized water, tetrahydrofuran (THF), the dissemination of dimethyl formamide to graphene oxide are identical, can be at identical conditions, obtain identical size classification, the mixed solution of any one or two or more arbitrary volume ratio therefore in deionized water, tetrahydrofuran (THF), dimethyl formamide also has identical dissemination, for the purpose of succinctly describing, separately do not enumerate in a specific embodiment.
Be to be understood that example as herein described and embodiment only in order to illustrate, those skilled in the art can make various amendment or change according to it, when not departing from spirit of the present invention, all belong to protection scope of the present invention.
Claims (10)
1. a preparation method for large lamella graphene oxide, comprises the following steps:
(1) with mixed acid solution, intercalation processing is carried out to natural flake graphite, obtain intercalated graphite, then intercalated graphite is heat-treated;
(2) carry out oxidizing reaction to through heat treated intercalated graphite, obtain graphene oxide;
(3) in graphene oxide, solvent is added, graphene oxide solution is made after abundant dissolving, then the pH value of graphene oxide solution is adjusted to < 7, finally adopts the method for standing process or centrifugal treating by the sedimentation of large lamella graphene oxide and separate.
2. the preparation method of large lamella graphene oxide as claimed in claim 1, is characterized in that: the carbon content of described natural flake graphite is 80-99.9%, and granularity is 80-500 orders.
3. the preparation method of large lamella graphene oxide as claimed in claim 1 or 2, it is characterized in that: described mixed acid solution is the nitration mixture of the vitriol oil and concentrated nitric acid or the strong phosphoric acid ratio mixing gained of 1-10:1 by volume, and the mass ratio of described mixed acid solution and natural flake graphite is 10-100:1.
4. the preparation method of lamella graphene oxide as claimed in claim 1 or 2 large, is characterized in that: the temperature of intercalation processing is room temperature, the time is 20-24h.
5. the preparation method of large lamella graphene oxide as claimed in claim 1 or 2, is characterized in that: heat treated temperature is 1000-1100 DEG C, the time is 12-17s.
6. the preparation method of lamella graphene oxide as claimed in claim 1 or 2 large, is characterized in that: described solvent is the mixed solution of any one or two or more arbitrary volume ratio in deionized water, tetrahydrofuran (THF), dimethyl formamide.
7. the preparation method of large lamella graphene oxide as claimed in claim 1 or 2, is characterized in that: the concentration of described graphene oxide solution is 0.1-10mg/ml.
8. the preparation method of large lamella graphene oxide as claimed in claim 1 or 2, is characterized in that: the pH value dilute hydrochloric acid of described graphene oxide solution or dilute sodium carbonate solution are adjusted to 2 ~ 6.
9. the preparation method of large lamella graphene oxide as claimed in claim 1 or 2, it is characterized in that: leave standstill the number of times of process more than once, the time of each process is 1 ~ 36h.
10. the preparation method of large lamella graphene oxide as claimed in claim 1 or 2, is characterized in that: the number of times of centrifugal treating is more than once, and the rotating speed of each process is 4000-10000rpm/min, and the time is 5-30min.
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| CN113213469A (en) * | 2021-05-31 | 2021-08-06 | 杭州高烯科技有限公司 | Equipment for preparing uniform small-size graphene oxide |
| CN115571874A (en) * | 2022-09-19 | 2023-01-06 | 成都飞机工业（集团）有限责任公司 | Large lamellar graphene oxide and preparation method thereof |
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