CN102583343A - Method for preparing graphene on large scale - Google Patents
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Abstract
The invention relates to a method for preparing graphene on large scale. The method comprises three steps of: oxidization of graphite, common intercalation of an oxidizing agent and a reducing agent among oxidized graphite sheet layers, and simultaneous expansion and reduction of the oxidized graphite caused by powerful reaction under specific temperature. The method has the advantages of low expansion temperature, simple process, low raw-material cost, high productivity and good reproducibility and the like, large-batch production is easy to realize, and the graphene prepared by using the method is widely used for the fields of high-performance composite materials, supercapacitors, lithium-ion batteries, fuel cells and micro-electronics and the like, and has wide application prospect.
Description
Technical field
The present invention relates to a kind of method for preparing Graphene in enormous quantities, belong to chemical technology field.
Background technology
Grapheme material is with a wide range of applications in fields such as microtronics, matrix material, transparent conductive film and energy storages because its unique two dimensional crystal structure has excellent machinery, optics, electricity and chemical property.Since 2004 are found by the Andre Geim of University of Manchester and Konstantin Novoselov first, (seen Novoselov KS, Geim AK, Morozov SV; Jiang D, Zhang Y, etal.Science; 2004,306,666); More and more receive the attention of scientific circles, and cause the climax of research Graphene in the world; Find that the earliest therefore two scientists of Graphene also win the Nobel Prize in physics in 2010 years.
Yet the prerequisite that the Graphene excellent properties is achieved is extensive, the low-cost preparation of grapheme material, and therefore, the technology of preparing of Graphene is ready-made to be the research focus of academia and engineering circle.Up to now, many physics and chemical process are used to prepare high-quality grapheme material, comprise that mainly graphite oxide reduction method, micromechanics peel off method, chemical Vapor deposition process and epitaxial growth method etc. and (see Berger C; Song Z, LiX.Science, 2006; 312,1191.; Tung VC, Allen MJ.Nature Nanotechnology, 2009,4,25.; Hernandez Y, Nicolosi V.Nature Nanotechnology, 2008,3,563.; Kim KS, ZhaoY.Nature, 2009,457,706.; Li X, Cai W.Science, 2009,324,1312.; ChoucairM, Thordarson P.Nature Nanotechnology, 2009,4,30.; Cai J, Ruffieux P.Nature, 2010,466,470).Wherein, micromechanics is peeled off method and is meant directly graphene platelet is stripped down from bigger crystal; Epitaxial growth method is meant that the molecule construction that will have a benzene ring structure through chemical reaction becomes to have the Graphene of big conjugated system; Chemical Vapor deposition process then is to remove Si through heating monocrystalline 6H-SiC, thereby on monocrystalline (001) face, decomposites the Graphene lamella; But these three kinds of methods all exist cost height and poor controllability, are not suitable for the mass preparation Graphene.The graphite oxide reduction method is meant carries out oxidation (strong acid strong oxidizer condition) to Graphite Powder 99, obtains graphene oxide after the supersound process; Again graphene oxide is prepared Graphene through the method for chemical reduction; Compare with first three methods, the major advantage of graphene oxide reduction method is that cost and energy consumption are low, and the Graphene productive rate is high, is one of graphene preparation method of paying close attention to the most at present, also is one of approach that most possibly realizes the Graphene mass production.Yet the industrialized prerequisite of this method is the preparation in enormous quantities of graphene oxide; But graphene oxide is a kind of two-dimensional slices shape structure, its good film-forming property, good dispersivity in water; And adopt methods such as common suction filtration, centrifugal settling or evaporation all to be difficult to it is separated from the aqueous solution.Therefore, for the large-scale industry preparation of Graphene, this method cost is high, efficient is low, thereby is unfavorable for applying.
At present, the production in enormous quantities of graphite oxide has caused that researcher pays close attention to widely.Wang Shimin etc. (see Wang Shimin, ten thousand is beautiful, etc.A kind of method of realizing large-scale preparation of monolayer oxidized graphene, CN 101591014B) proposed to peel off graphite oxide is ultrasonic, the graphite oxide flocculating settling after will peeling off again comes mass to obtain the method for mono-layer graphite oxide alkene.But products obtained therefrom is a graphene oxide, needs further reduction just can be transformed into Graphene truly; In addition, the peeling off on the basis that still is based upon ultrasonic technique of graphite oxide in this method, because of ultrasonic peeling off itself is exactly the process of a length consuming time, thereby not from the problem of the production in enormous quantities that solves grapheme material in essence.Chen Guohuas etc. (are seen Chen Guohua, Fang Ming, Zhao Liping.A kind of method for preparing Graphene in enormous quantities, CN 102167311A) proposes employing graphite oxidation-flocculating settling-three steps of pyroprocessing and come preparation Graphene in enormous quantities.But this method exists the length consuming time, graphene oxide need be through problems such as high temperature reductions equally, and this method is high to the requirement of equipment, is difficult to realize preparation in enormous quantities.
To the problem that existing in enormous quantities preparation Graphene exists, a kind of a large amount of methods that prepare Graphene of simple and practical, economical and efficient are provided, thereby the production in enormous quantities that solves Graphene have important application and academic significance.
Summary of the invention
In order to overcome the deficiency that prior art exists, the object of the present invention is to provide a kind of a large amount of methods that prepare Graphene of simple and practical, economical and efficient, thus the production in enormous quantities that solves Graphene.
For reaching the foregoing invention purpose, the technical scheme that the present invention adopts is:
A kind of method for preparing Graphene in enormous quantities is provided, and it is characterized in that: the step of said preparation Graphene in enormous quantities comprises: the 1) oxidation of graphite; 2) oxygenant and reductive agent are at the common intercalation of oxidized graphite flake interlayer; 3) expand the vigorous reaction initiated oxidation graphite under the specified temp time and reduction.
The oxidation of said graphite is the mixed solution that Graphite Powder 99 is placed strong acid and strong oxidizer, after 25-100 ℃ of following oxidation 0.1-120 hour, and dilute with water; Add a certain amount of hydrogen peroxide; Filtered while hot uses Hydrogen chloride and deionized water wash to neutral again, obtains graphite oxide after the drying.
Described strong acid is a kind of in the vitriol oil, concentrated nitric acid and the perchloric acid, or their combination; Described strong oxidizer is a kind of in potassium permanganate, Potcrate, VAL-DROP, Potassium Persulphate, SODIUMNITRATE and the SRM 935a, or their combination.
Said oxygenant and reductive agent comprise in the step of the common intercalation of oxidized graphite flake interlayer: 1) 10 parts of graphite oxides being added 10-1000 part oxygenant mass percent concentration is the aqueous solution of 0.5-98%; Soak the 0.01-120h postcooling down to room temperature at 0-100 ℃; After filtration, vacuum-drying, obtain containing the graphite oxide of oxygenant; 2) will contain in the graphite oxide adding reductive agent of oxygenant, soak 0.001-120h down, after filtering, obtain the graphite oxide of oxygenant and reductive agent intercalation at 0-35 ℃.
Described oxygenant is a kind of in nitric acid, sulfuric acid and the perchloric acid, or their combination; Described reductive agent is that acetone, ethanol and methyl alcohol etc. have a kind of in the organic solvent of reductibility or their combination.
Expand in the time of vigorous reaction initiated oxidation graphite under the said specified temp and reduction system handles 0.001-120h with the atmosphere furnace that the graphite oxide of oxygenant and reductive agent intercalation places temperature to be higher than 50 ℃, promptly get the graphene powder of high loft.
Said atmosphere is a kind of in oxygen, air, nitrogen, argon gas, helium and the hydrogen, or their combination.
Compared with prior art; The beneficial effect that the present invention obtains is: 1) the violent small molecules that oxidation-reduction reaction generated can make graphite oxide expand rapidly and peel off into graphene oxide; Because its level of response is controlled, thereby the extent of exfoliation of graphite oxide is controlled equally; 2) oxidation-reduction reaction can produce great amount of heat simultaneously, and the temperature of graphite oxide is risen sharp; And under the synergy of heat and reductive agent, realize peeling off and reducing of graphite oxide simultaneously; 3) expansion temperature required for the present invention is low, technology is simple, raw materials cost is cheap, productive rate is higher, favorable reproducibility, is easy to realize producing in enormous quantities.Based on above-mentioned advantage, the grapheme material that the present invention prepares can be used for high performance composite, ultracapacitor, lithium ion battery, and fields such as fuel cell and microelectronics are with a wide range of applications.
Description of drawings
Fig. 1 is the FTIR spectrogram of the embodiment of the invention 1 prepared graphene;
Fig. 2 is the XRD spectra of the embodiment of the invention 1 prepared graphene;
Fig. 3 is the Raman spectrogram of the embodiment of the invention 1 prepared graphene;
Fig. 4 is the TEM spectrogram of the embodiment of the invention 1 prepared graphene;
Fig. 5 is the TG spectrogram of the embodiment of the invention 1 prepared graphene;
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment 1
The first step (oxidation of graphite): with 10g graphite, 230mL mass percent concentration is that the mixing of 98% vitriol oil places ice bath, stirs it is mixed, and then, takes by weighing 40g potassium permanganate and adds above-mentioned mixed solution, under 35 ℃ of conditions, reacts 2h; 500mL water is added the ydrogen peroxide 50 that adds 100mL after the above-mentioned reaction system, treat that solution is glassy yellow after, filtered while hot; At last, extremely neutral with Hydrogen chloride and water washing, obtain graphite oxide after the vacuum-drying.
Second step (oxygenant and reductive agent are at the common intercalation of oxidized graphite flake interlayer): 1) with the resulting graphite oxide of 10g step 1 adding 100g mass percent concentration be 90% nitric acid; Soak the 2h postcooling down to room temperature at 35 ℃, after filtration, vacuum-drying, obtain containing the graphite oxide of nitric acid; 2) will contain in the graphite oxide adding acetone of nitric acid, soak 1h down, after filtering, obtain the graphite oxide of nitric acid and acetone intercalation at 25 ℃.
The 3rd step (expanding in the time of vigorous reaction initiated oxidation graphite specified temp under and reduction): after the nitric acid that 10g step 2 is obtained and the graphite oxide of acetone intercalation place 100 ℃ air atmosphere stove processing 0.01h, promptly get the graphene powder of black, high loft.
The specific surface area of the graphene powder of gained is 421m2/g; Its FT-IR, XRD, Raman, TEM and TG spectrogram are like Fig. 1,2,3, shown in 4 and 5.
The first step (oxidation of graphite): with 10g graphite, 100mL mass percent concentration is that the mixing of 90% vitriol oil places ice bath, stirs it is mixed, and then, takes by weighing the 10g SRM 935a and adds above-mentioned mixed solution, under 25 ℃ of conditions, reacts 0.1h; After 100mL water added above-mentioned reaction system, filtered while hot; At last, extremely neutral with Hydrogen chloride and water washing, obtain graphite oxide after the vacuum-drying.
Second step (oxygenant and reductive agent are at the common intercalation of oxidized graphite flake interlayer): 1) with the resulting graphite oxide of 10g step 1 adding 10g mass percent concentration be 0.5% nitric acid; Soak the 0.01h postcooling down to room temperature at 0 ℃, after filtration, vacuum-drying, obtain containing the graphite oxide of nitric acid; 2) will contain in the graphite oxide adding acetone of nitric acid, soak 0.001h down, after filtering, obtain the graphite oxide of nitric acid and acetone intercalation at 0 ℃.
The 3rd step (expanding in the time of vigorous reaction initiated oxidation graphite specified temp under and reduction): after the nitric acid that 10g step 2 is obtained and the graphite oxide of acetone intercalation place 50 ℃ oxygen atmosphere stove processing 1h, promptly get the graphene powder of black, high loft.
Embodiment 3
The first step (oxidation of graphite): with 10g graphite, 1000mL mass percent concentration is that the mixing of 60% concentrated nitric acid places ice bath, stirs it is mixed, and then, takes by weighing 100g Potcrate and adds above-mentioned mixed solution, under 100 ℃ of conditions, reacts 120h; 10000mL water is added the ydrogen peroxide 50 that adds 1000mL after the above-mentioned reaction system, treat that solution is glassy yellow after, filtered while hot; At last, extremely neutral with Hydrogen chloride and water washing, obtain graphite oxide after the vacuum-drying.
Second step (oxygenant and reductive agent are at the common intercalation of oxidized graphite flake interlayer): 1) with the resulting graphite oxide of 10g step 1 adding 1000g mass percent concentration be 98% sulfuric acid; Soak the 120h postcooling down to room temperature at 100 ℃, after filtration, vacuum-drying, obtain vitriolated graphite oxide; 2) vitriolated graphite oxide is added in the ethanol, soak 120h down, after filtering, obtain the graphite oxide of sulfuric acid and ethanol intercalation at 35 ℃.
The 3rd step (expanding in the time of vigorous reaction initiated oxidation graphite specified temp under and reduction): after the sulfuric acid that 10g step 2 is obtained and the graphite oxide of ethanol intercalation place 110 ℃ argon gas atmosphere stove processing 120h, promptly get the graphene powder of black, high loft.
Embodiment 4
The first step (oxidation of graphite): with 10g graphite, 300mL mass percent concentration is that the mixing of 65% nitric acid places ice bath, stirs it is mixed, and then, takes by weighing 50g VAL-DROP and adds above-mentioned mixed solution, under 55 ℃ of conditions, reacts 3h; 1000mL water is added the ydrogen peroxide 50 that adds 200mL after the above-mentioned reaction system, treat that solution is glassy yellow after, filtered while hot; At last, extremely neutral with Hydrogen chloride and water washing, obtain graphite oxide after the vacuum-drying.
Second step (oxygenant and reductive agent are at the common intercalation of oxidized graphite flake interlayer): 1) with the resulting graphite oxide of 10g step 1 adding 200g mass percent concentration be 60% perchloric acid; Soak the 1h postcooling down to room temperature at 45 ℃, after filtration, vacuum-drying, obtain containing the graphite oxide of perchloric acid; 2) will contain in the graphite oxide adding methyl alcohol of perchloric acid, soak 2h down, after filtering, obtain the graphite oxide of perchloric acid and methyl alcohol intercalation at 35 ℃.
The 3rd step (expanding in the time of vigorous reaction initiated oxidation graphite specified temp under and reduction): after the perchloric acid that 10g step 2 is obtained and the graphite oxide of methyl alcohol intercalation place 400 ℃ nitrogen atmosphere stove processing 0.001h, promptly get the graphene powder of black, high loft.
Embodiment 5
The first step (oxidation of graphite): with 10g graphite, 350mL mass percent concentration is that the mixing of 70% perchloric acid places ice bath, stirs it is mixed, and then, takes by weighing the 50g Potassium Persulphate and adds above-mentioned mixed solution, under 65 ℃ of conditions, reacts 2.5h; 1500mL water is added the ydrogen peroxide 50 that adds 250mL after the above-mentioned reaction system, treat that solution is glassy yellow after, filtered while hot; At last, extremely neutral with Hydrogen chloride and water washing, obtain graphite oxide after the vacuum-drying.
Second step (oxygenant and reductive agent are at the common intercalation of oxidized graphite flake interlayer): 1) with the resulting graphite oxide of 10g step 1 adding 300g mass percent concentration be 50% nitric acid and vitriolic mixed solution (nitric acid and vitriolic mass ratio are 2: 1); Soak the 2h postcooling down to room temperature at 55 ℃, after filtration, vacuum-drying, obtain containing nitric acid and vitriolic graphite oxide; 2) will contain nitric acid and vitriolic graphite oxide and add in the acetone, soak 1h down, after filtering, obtain the graphite oxide of nitric acid, sulfuric acid and acetone intercalation at 25 ℃.
The 3rd step (expanding in the time of vigorous reaction initiated oxidation graphite specified temp under and reduction): after the graphite oxide of nitric acid, sulfuric acid and the acetone intercalation that 10g step 2 is obtained places 85 ℃ helium atmosphere stove processing 0.02h, promptly get the graphene powder of black, high loft.
Embodiment 6
The first step (oxidation of graphite): with 10g graphite, 350mL mass percent concentration is that the mixing of 60% perchloric acid places ice bath; Stirring mixes it; Then, take by weighing 20g SODIUMNITRATE and the 30g SRM 935a adds above-mentioned mixed solution, under 65 ℃ of conditions, react 2.5h; 1500mL water is added the ydrogen peroxide 50 that adds 250mL after the above-mentioned reaction system, treat that solution is glassy yellow after, filtered while hot; At last, extremely neutral with Hydrogen chloride and water washing, obtain graphite oxide after the vacuum-drying.
Second step (oxygenant and reductive agent are at the common intercalation of oxidized graphite flake interlayer): be in 40% the nitric acid 1) with the resulting graphite oxide of 10g step 1 adding 100g mass percent concentration; Soak the 2h postcooling down to room temperature at 65 ℃, after filtration, vacuum-drying, obtain containing the graphite oxide of nitric acid; The graphite oxide that 2) will contain nitric acid adds in the mixed solution (volume ratio of acetone and methyl alcohol is 2: 1) of acetone and methyl alcohol, at 25 ℃ times immersion 1h, after filtering, obtains the graphite oxide of nitric acid and acetone intercalation.
The 3rd step (expanding in the time of vigorous reaction initiated oxidation graphite specified temp under and reduction): after the graphite oxide of nitric acid, acetone and the methyl alcohol intercalation that 10g step 2 is obtained places 95 ℃ oxygen and nitrogen blended atmosphere furnace (volume ratio of nitrogen and oxygen is 9: 1) processing 0.02h, promptly get the graphene powder of black, high loft.
Embodiment 7
The first step (oxidation of graphite): with 10g graphite, 150mL mass percent concentration is that 60% perchloric acid and 200mL mass percent concentration are that 70% sulfuric acid mixes and places ice bath; Stirring mixes it; Then; Take by weighing 70g SODIUMNITRATE and add above-mentioned mixed solution, under 75 ℃ of conditions, react 1.5h; 2000mL water is added the ydrogen peroxide 50 that adds 1500mL after the above-mentioned reaction system, treat that solution is glassy yellow after, filtered while hot; At last, extremely neutral with Hydrogen chloride and water washing, obtain graphite oxide after the vacuum-drying.
Second step (oxygenant and reductive agent are at the common intercalation of oxidized graphite flake interlayer): be in 30% the nitric acid 1) with the resulting graphite oxide of 10g step 1 adding 300g mass percent concentration; Soak the 1h postcooling down to room temperature at 85 ℃, after filtration, vacuum-drying, obtain containing the graphite oxide of nitric acid; 2) will contain in the graphite oxide adding methyl alcohol of nitric acid, soak 1h down, after filtering, obtain the graphite oxide of nitric acid and methyl alcohol intercalation at 15 ℃.
The 3rd step (expanding in the time of vigorous reaction initiated oxidation graphite specified temp under and reduction): after the nitric acid that 10g step 2 is obtained and the graphite oxide of methyl alcohol intercalation place 75 ℃ hydrogen atmosphere stove processing 0.01h, promptly get the graphene powder of black, high loft.
Referring to Fig. 1, it is the FTIR spectrogram of the grapheme material of the embodiment of the invention 1 preparation; Referring to Fig. 2, it is the XRD spectra of the embodiment of the invention 1 prepared graphene; Referring to Fig. 3, it is the Raman spectrogram of the embodiment of the invention 1 prepared graphene; Referring to Fig. 4, it is the TEM spectrogram of the embodiment of the invention 1 prepared graphene.Can find out that from Fig. 1, Fig. 2, Fig. 3 and Fig. 4 prepared graphene material of the present invention is peeled off fully with reduction and become grapheme material;
Referring to Fig. 5, it is the TG spectrogram of the embodiment of the invention 1 prepared graphene.As can beappreciated from fig. 5, compare with graphite oxide, prepared graphene material of the present invention has more excellent thermostability.
Claims (7)
1. method for preparing in enormous quantities Graphene, it is characterized in that: the step of said preparation Graphene in enormous quantities comprises: the 1) oxidation of graphite; 2) oxygenant and reductive agent are at the common intercalation of oxidized graphite flake interlayer; 3) expand the vigorous reaction initiated oxidation graphite under the specified temp time and reduction.
2. a kind of method for preparing Graphene in enormous quantities according to claim 1; It is characterized in that: the oxidation of said graphite is the mixed solution that Graphite Powder 99 is placed strong acid and strong oxidizer, after 25-100 ℃ of following oxidation 0.1-120 hour, and dilute with water; Add a certain amount of hydrogen peroxide; Filtered while hot uses Hydrogen chloride and deionized water wash to neutral again, obtains graphite oxide after the drying.
3. a kind of method for preparing Graphene in enormous quantities according to claim 2 is characterized in that: described strong acid is a kind of in the vitriol oil, concentrated nitric acid and the perchloric acid, or their combination; Described strong oxidizer is a kind of in potassium permanganate, Potcrate, VAL-DROP, Potassium Persulphate, SODIUMNITRATE and the SRM 935a, or their combination.
4. a kind of method for preparing Graphene in enormous quantities according to claim 1; It is characterized in that: said oxygenant and reductive agent comprise in the step of the common intercalation of oxidized graphite flake interlayer: 1) 10 parts of graphite oxides being added 10-1000 part oxygenant mass percent concentration is the aqueous solution of 0.5-98%; Soak the 0.01-120h postcooling down to room temperature at 0-100 ℃; After filtration, vacuum-drying, obtain containing the graphite oxide of oxygenant; 2) will contain in the graphite oxide adding reductive agent of oxygenant, soak 0.001-120h down, after filtering, obtain the graphite oxide of oxygenant and reductive agent intercalation at 0-35 ℃.
5. a kind of method for preparing Graphene in enormous quantities according to claim 6 is characterized in that: described oxygenant is a kind of in nitric acid, sulfuric acid and the perchloric acid, or their combination; Described reductive agent is that acetone, ethanol and methyl alcohol etc. have a kind of in the organic solvent of reductibility or their combination.
6. a kind of method for preparing Graphene in enormous quantities according to claim 1; It is characterized in that: expand in the time of vigorous reaction initiated oxidation graphite under the said specified temp and reduction system handles 0.001-120h with the atmosphere furnace that the graphite oxide of oxygenant and reductive agent intercalation places temperature to be higher than 50 ℃, promptly get the graphene powder of high loft.
7. a kind of method for preparing Graphene in enormous quantities according to claim 6 is characterized in that: said atmosphere is a kind of in oxygen, air, nitrogen, argon gas, helium and the hydrogen, or their combination.
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| CN103407995A (en) * | 2013-07-17 | 2013-11-27 | 苏州艾特斯环保材料有限公司 | Graphite oxide preparation method |
| CN103449424A (en) * | 2012-08-28 | 2013-12-18 | 武汉大学 | Low temperature preparation method of graphene and graphene-based composite material |
| CN103553033A (en) * | 2013-11-11 | 2014-02-05 | 河北大学 | Method for preparing graphene material |
| CN103613093A (en) * | 2013-11-25 | 2014-03-05 | 黄德欢 | Method for preparing graphene through hydrogen gas reduction |
| CN103833008A (en) * | 2012-11-20 | 2014-06-04 | 中国科学院兰州化学物理研究所 | Method for preparing graphene at normal temperature |
| CN106802295A (en) * | 2017-03-16 | 2017-06-06 | 合肥学院 | A kind of chemical preparation process of the graphene quantum dot fluorescence probe to trace TNT detections |
| CN109666350A (en) * | 2017-10-16 | 2019-04-23 | 山东欧铂新材料有限公司 | A kind of waterborne conductive coating and preparation method thereof containing highly conductive graphene |
| CN110902671A (en) * | 2019-10-18 | 2020-03-24 | 东北大学 | Preparation method of low-layer graphene |
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| CN106802295A (en) * | 2017-03-16 | 2017-06-06 | 合肥学院 | A kind of chemical preparation process of the graphene quantum dot fluorescence probe to trace TNT detections |
| CN109666350A (en) * | 2017-10-16 | 2019-04-23 | 山东欧铂新材料有限公司 | A kind of waterborne conductive coating and preparation method thereof containing highly conductive graphene |
| CN109666350B (en) * | 2017-10-16 | 2021-06-29 | 山东欧铂新材料有限公司 | Water-based conductive coating containing high-conductivity graphene and preparation method thereof |
| CN110902671A (en) * | 2019-10-18 | 2020-03-24 | 东北大学 | Preparation method of low-layer graphene |
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