CN107032337A - The method that commercial graphites alkene is produced with oxidation-reduction method - Google Patents
The method that commercial graphites alkene is produced with oxidation-reduction method Download PDFInfo
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- CN107032337A CN107032337A CN201710461328.7A CN201710461328A CN107032337A CN 107032337 A CN107032337 A CN 107032337A CN 201710461328 A CN201710461328 A CN 201710461328A CN 107032337 A CN107032337 A CN 107032337A
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- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
Abstract
The invention belongs to new material field of preparation of graphene, and in particular to a kind of method that commercial graphites alkene is produced with oxidation-reduction method.The described method that commercial graphites alkene is produced with oxidation-reduction method, step is as follows：(1) pretreatment of raw material：After the concentrated sulfuric acid is mixed with natural flake graphite, temperature reaction obtains acidic mixed material；(2) aoxidize：After acidic mixed material is cooled, sequentially add potassium permanganate, water and reacted, reaction is finished, add hydrogen peroxide, obtain graphite oxide solution；(3) wash：Centrifugation, washing graphite oxide solution to neutrality；(4) it is ultrasonic：Step (3) resulting solution is formulated as suspension, ultrasound obtains graphene oxide solution；(5) reduce：Hydration hydrazine reaction is added after graphene oxide solution is heated up, dries, crush, obtain graphene solid powder.The method of the invention is with short production cycle, yield is high, production cost is low, be easily achieved industrialization.
Description
Technical field
The invention belongs to new material field of preparation of graphene, and in particular to a kind of to produce commercial graphites alkene with oxidation-reduction method
Method.
Background technology
Graphene be it is a kind of by carbon atom with sp2 hybridized orbits constitute hexangle type be in honeycomb lattice flat film, only
The two-dimensional material of one carbon atom thickness, be in the world it is most thin be but also most hard nano material.It is widely used in electronic device, gas
The fields such as body sensor, semiconductor chip, solar cell, high strength shell material and composite.
From 2004, the time of a few years, researcher just achieved positive development in terms of the preparation of graphene,
It is found that a variety of preparation methods such as mechanical stripping, crystal epitaxy, redox, chemical vapor deposition, these preparation methods
There are respective advantage and disadvantage, micromechanics stripping method is simple, can obtain the graphene of high-quality, but poor repeatability, yield and yield
It is very low；Graphene prepared by chemical vapour deposition technique has a more complete crystal structure, and graphene area is big, in transparency electrode and
The fields such as electronic equipment show apparent application advantage, but it is relatively low to there is yield, high expensive, and graphene hardly possible transfer etc. lacks
Point；Surface epitaxial growth can prepare the single-layer graphene of large area, but this method preparation condition it is harsh, it is necessary to high temperature and
High vacuum, and graphene hardly possible be transferred out from substrate.
Current oxidation-reduction method be it is generally acknowledged can industrialized production graphene method, but there is also many bright for this method
Aobvious shortcoming：One is that water consumption is big, does not meet present environmental protection theory when washing graphite oxide；Two be to match somebody with somebody oxygenerating stone
During black suspension, after graphite oxide solution is freeze-dried, plus appropriate pure water is prepared, and is so extended manufacture cycle, is added to
This, is not suitable for industrial production；Three be that graphene is dried using the method being freeze-dried, and freeze-drying batch is generally arid cycle
48 hours, arid cycle was long, and high equipment cost, and every batch of dry amount is few, so inadvisable in industrialized production.In addition,
It is puffy to be freeze-dried the graphene material drawn, and bulk density is 0.15~0.28g/cm3, bulk density is too small to be influenceed
The charge/discharge rates of battery.
The content of the invention
In view of the shortcomings of the prior art, with oxidation-reduction method commercial graphites alkene is produced it is an object of the invention to provide a kind of
Method, the graphene bulk density of preparation is high, and methods described has that with short production cycle, yield is high, production cost is low, be easily achieved
Industrialized feature.
The method of the present invention that commercial graphites alkene is produced with oxidation-reduction method, step is as follows：
(1) pretreatment of raw material：
After the concentrated sulfuric acid is mixed with natural flake graphite, temperature reaction obtains acidic mixed material；
(2) aoxidize：
After acidic mixed material is cooled, sequentially add potassium permanganate, water and reacted, reaction is finished, add hydrogen peroxide,
Obtain graphite oxide solution；
(3) wash：
Centrifugation, washing graphite oxide solution to neutrality；
(4) it is ultrasonic：
Step (3) resulting solution is formulated as suspension, ultrasound obtains graphene oxide solution；
(5) reduce：
Hydration hydrazine reaction is added after graphene oxide solution is heated up, dries, crush, obtain graphene solid powder.
Wherein：
In step (1), the described concentrated sulfuric acid and the mass ratio of natural flake graphite are 100:1~150:1.Preferably, it is dense
The mass ratio of sulfuric acid and natural flake graphite is 110:1.
In step (1), described reaction temperature is 75~85 DEG C, and the reaction time is 2~4 hours.
In step (2), described cooling is to be cooled to 0~20 DEG C.
In step (2), the addition of described potassium permanganate is 2~9 times of natural flake graphite quality.Preferably, it is high
The addition of potassium manganate is 5 times of natural flake graphite quality.Described potassium permanganate is slowly added in acidic mixed material, control
System was added in 1.5~2 hours.Described water is slowly added in acidic mixed material, and control was added in 4~6 hours.Gao Meng
Sour potassium adds too fast easy generation local reaction, the influence graphene number of plies and particle diameter.
In step (2), described reaction temperature is 35~45 DEG C, and the reaction time is 2~3 hours.The too low meeting of reaction temperature
Cause reaction insufficient, influence reaction yield；Reaction temperature is more than 50 DEG C, and the material of generation is easily crosslinked, the ring on carbocyclic ring
Oxygen Guan Nengtuan becomes many, should not reduce, directly affect the performance of graphene.
In step (2), add after hydrogen peroxide, solution is changed into golden yellow.
In step (3), centrifugation, the water of washing, classified storage repeat to use, and using water wisely reduces sewage yield, entered
And reduce cost.Dilute acid soln (containing a small amount of material) classified storage after the present invention centrifuges gained in water-washing process is precipitated,
The material collection for taking supernatant to be repeatedly used for after washing, precipitation, so often production 1kg graphenes are economized on water 5 tons, the yield of graphene
5% or so is improved, cost will be low by 7.5%, meets green and environmental protection concept.
In step (4), the concentration of described suspension is 1~8g/L, and described ultrasonic time is 20~30 minutes.It is preferred that
Ground, the concentration of described suspension is 5g/L.
In step (5), the addition of described hydrazine hydrate is 6~15 times of graphene oxide solution solid content.Preferably,
The addition of described hydrazine hydrate is 12 times of graphene oxide solution solid content, and described hydrazine hydrate is slowly added to oxidation stone
In black alkene solution, control was added in 2~4 hours.
In step (5), graphene oxide solution is warming up to after 60~80 DEG C and adds hydrazine hydrate, sustained response 8~13 is small
When.
In step (5), described drying is microwave drying.Described microwave drying is done to be put into microwave dryer
It is dry, dry to it is aqueous be less than 1% untill.The present invention uses the arid cycle of microwave drying for 2 hours, dries a batches section
Make an appointment 46 hours, drying efficiency is original 23 times, drying cost reduction by 80%.
There is microwave penetration performance to make medium is inside and outside to heat simultaneously in microwave drying, it is not necessary to heat transfer, so heating speed
Degree is very fast, and rate of drying can shorten hundreds times.Simultaneously regardless of object any shape, due to adding inside and outside the medium of object simultaneously
Heat, the internal-external temperature difference of material is small, homogeneous heating, will not produce and occur scorched outside and underdone inside situation in conventional heating, make dry mass
Greatly improve.
The oxygen-containing functional group that microwave drying can not be reduced graphene using microwave, is got rid of using microwave so that
The oxygen content of graphene is substantially reduced.Too high oxygen level can influence the application in terms of battery, therefore, microwave drying in graphene
More than simple drying, also reduces the effect of graphene oxygen content.
The present invention compared with prior art, has the advantages that：
1st, the present invention passes through the defect with concentrated sulfuric acid removal graphite in itself under pretreatment of raw material stage, high temperature, makes graphite
Lamella is regular；Hydrogen sulfate ion adds spacing between layers in graphite flake layer intercalation, and function is aoxidized beneficial to next step
Group's insertion, is easy to ultrasonic delamination, and the graphene number of plies of production is at 5-8 layers, and every batch of product is stable.
2nd, formulated suspension process saves time of the present invention, cost-effective.Process of the common laboratory in configuration suspension
It is the graphite oxide solution freeze-drying this batch of production, weighs, calculate amount of water.It is well known that sublimation drying is 24-48
Hour, influence the production capacity of production line.In industrialized production, prepared according to mode of the present invention, graphene can be made to prepare cost drop
Low 5-8%, production capacity improves 10%, meets energy-saving objective.
3rd, the present invention uses microwave drying, and arid cycle is short, drying cost is low, and the graphene bulk density of preparation is 0.80
~1.0g/cm3。
4th, graphene is typically industrially prepared with oxidation-reduction method now, the oxygen-containing graphene after reduction is 15~20%,
The oxygen content of graphene is constant after freeze-drying, and the graphene oxygen content after microwave drying is 5~8%, and oxygen content reduction 7~
15%.Too high oxygen level in graphene, can influence the application in terms of battery, super capacitor.
5th, the method for the invention yield reaches 80~90%, and with short production cycle, production cost is low, be easily achieved industry
Change.
Brief description of the drawings
Fig. 1 is the production technological process of the present invention.
Embodiment
With reference to embodiment, the present invention will be further described.
Embodiment 1
The described method that commercial graphites alkene is produced with oxidation-reduction method, step is as follows：
(1) pretreatment of raw material：
After the concentrated sulfuric acid is mixed with natural flake graphite, it is warming up to 80 DEG C and reacts 3 hours, obtain acidic mixed material；It is described
The concentrated sulfuric acid and natural flake graphite mass ratio be 110:1.
(2) aoxidize：
Acidic mixed material is cooled to after 10 DEG C, potassium permanganate, water is sequentially added and reacts 2.5 hours at 40 DEG C, instead
It should finish, add hydrogen peroxide, obtain graphite oxide solution；The addition of described potassium permanganate is the 5 of natural flake graphite quality
Times, potassium permanganate is slowly added in acidic mixed material, and control was added in 1.8 hours；Described water is slowly added to acid mixed
In compound material, control was added in 5 hours；The addition of described hydrogen peroxide is 0.7 times of potassium permanganate quality.
(3) wash：
Centrifugation, washing graphite oxide solution to neutrality；
(4) it is ultrasonic：
Step (3) resulting solution is formulated as the suspension that concentration is 5g/L, ultrasound 25 minutes obtains graphene oxide molten
Liquid；
(5) reduce：
Graphene oxide solution is warming up to after 70 DEG C and adds hydrazine hydrate sustained response 10 hours, microwave drying, crushing are obtained
Graphene solid powder, yield is 90%, and bulk density is 1.0g/cm3.The addition of described hydrazine hydrate is graphene oxide
10 times of solution solid content；Described hydrazine hydrate controls to add in 3 hours.
Embodiment 2
The described method that commercial graphites alkene is produced with oxidation-reduction method, step is as follows：
(1) pretreatment of raw material：
After the concentrated sulfuric acid is mixed with natural flake graphite, it is warming up to 75 DEG C and reacts 4 hours, obtain acidic mixed material；It is described
The concentrated sulfuric acid and natural flake graphite mass ratio be 100:1.
(2) aoxidize：
Acidic mixed material is cooled to after 0 DEG C, potassium permanganate, water is sequentially added and is reacted 3 hours at 35 DEG C, reacted
Finish, add hydrogen peroxide, obtain graphite oxide solution；The addition of described potassium permanganate is 2 times of natural flake graphite quality, high
Potassium manganate is slowly added in acidic mixed material, and control was added in 1.5 hours；Described water is slowly added to acidic mixed material
In, control was added in 4 hours；The addition of described hydrogen peroxide is 0.4 times of potassium permanganate quality.
(3) wash：
Centrifugation, washing graphite oxide solution to neutrality；
(4) it is ultrasonic：
Step (3) resulting solution is formulated as the suspension that concentration is 1g/L, ultrasound 20 minutes obtains graphene oxide molten
Liquid；
(5) reduce：
Graphene oxide solution is warming up to after 60 DEG C and adds hydrazine hydrate sustained response 13 hours, microwave drying, crushing are obtained
Graphene solid powder, yield is 80%, and bulk density is 0.85g/cm3.The addition of described hydrazine hydrate is graphite oxide
6 times of alkene solution solid content.Described hydrazine hydrate controls to add in 2 hours.
Embodiment 3
The described method that commercial graphites alkene is produced with oxidation-reduction method, step is as follows：
(1) pretreatment of raw material：
After the concentrated sulfuric acid is mixed with natural flake graphite, it is warming up to 85 DEG C and reacts 2 hours, obtain acidic mixed material；It is described
The concentrated sulfuric acid and natural flake graphite mass ratio be 150:1.
(2) aoxidize：
Acidic mixed material is cooled to after 20 DEG C, potassium permanganate, water is sequentially added and is reacted 2 hours at 45 DEG C, is reacted
Finish, add hydrogen peroxide, obtain graphite oxide solution；The addition of described potassium permanganate is 9 times of natural flake graphite quality,
Potassium permanganate is slowly added in acidic mixed material, and control was added in 2 hours；Described water is slowly added to acidic mixed material
In, control was added in 6 hours；The addition of described hydrogen peroxide is 1 times of potassium permanganate quality.
(3) wash：
Centrifugation, washing graphite oxide solution to neutrality；
(4) it is ultrasonic：
Step (3) resulting solution is formulated as the suspension that concentration is 8g/L, ultrasound 30 minutes obtains graphene oxide molten
Liquid；
(5) reduce：
Graphene oxide solution is warming up to after 80 DEG C and adds hydrazine hydrate sustained response 8 hours, microwave drying, crushing are obtained
Graphene solid powder, yield is 85%, and bulk density is 0.9g/cm3.The addition of described hydrazine hydrate is graphene oxide
15 times of solution solid content.Described hydrazine hydrate controls to add in 4 hours.
Claims (10)
1. a kind of method that commercial graphites alkene is produced with oxidation-reduction method, it is characterised in that：Step is as follows：
(1) pretreatment of raw material：
After the concentrated sulfuric acid is mixed with natural flake graphite, temperature reaction obtains acidic mixed material；
(2) aoxidize：
After acidic mixed material is cooled, sequentially add potassium permanganate, water and reacted, reaction is finished, add hydrogen peroxide, obtain oxygen
Graphite solution；
(3) wash：
Centrifugation, washing graphite oxide solution to neutrality；
(4) it is ultrasonic：
Step (3) resulting solution is formulated as suspension, ultrasound obtains graphene oxide solution；
(5) reduce：
Hydration hydrazine reaction is added after graphene oxide solution is heated up, dries, crush, obtain graphene solid powder.
2. the method according to claim 1 that commercial graphites alkene is produced with oxidation-reduction method, it is characterised in that：Step (1)
In, the described concentrated sulfuric acid and the mass ratio of natural flake graphite are 100:1~150:1.
3. the method according to claim 1 that commercial graphites alkene is produced with oxidation-reduction method, it is characterised in that：Step (1)
In, described reaction temperature is 75~85 DEG C, and the reaction time is 2~4 hours.
4. the method according to claim 1 that commercial graphites alkene is produced with oxidation-reduction method, it is characterised in that：Step (2)
In, described cooling is is cooled to 0~20 DEG C, and the addition of described potassium permanganate is the 2~9 of natural flake graphite quality
Times.
5. the method according to claim 1 that commercial graphites alkene is produced with oxidation-reduction method, it is characterised in that：Step (2)
In, described reaction temperature is 35~45 DEG C, and the reaction time is 2~3 hours.
6. the method according to claim 1 that commercial graphites alkene is produced with oxidation-reduction method, it is characterised in that：Step (2)
In, the addition of described hydrogen peroxide is 0.4~1 times of potassium permanganate quality.
7. the method according to claim 1 that commercial graphites alkene is produced with oxidation-reduction method, it is characterised in that：Step (4)
In, the concentration of described suspension is 1~8g/L, and described ultrasonic time is 20~30 minutes.
8. the method according to claim 1 that commercial graphites alkene is produced with oxidation-reduction method, it is characterised in that：Step (5)
In, the addition of described hydrazine hydrate is 6~15 times of graphene oxide solution solid content.
9. the method according to claim 1 that commercial graphites alkene is produced with oxidation-reduction method, it is characterised in that：Step (5)
In, graphene oxide solution is warming up to after 60~80 DEG C and adds hydrazine hydrate, sustained response 8~13 hours.
10. the method according to claim 1 that commercial graphites alkene is produced with oxidation-reduction method, it is characterised in that：Step (5)
In, described drying is microwave drying.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892043A (en) * | 2020-08-06 | 2020-11-06 | 昆明理工大学 | Method for preparing reduced graphene oxide by one-pot method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941694A (en) * | 2010-09-07 | 2011-01-12 | 湘潭大学 | Preparation method of high-dispersivity graphene |
| CN102173414A (en) * | 2011-03-18 | 2011-09-07 | 中国地质大学（武汉） | Method for preparing graphene oxide by chemical peeling |
| CN102491318A (en) * | 2011-12-13 | 2012-06-13 | 河北工业大学 | Method for preparing graphene oxide |
| CN102502611A (en) * | 2011-11-15 | 2012-06-20 | 东南大学 | Method for rapidly preparing graphene in large quantities by utilizing graphite oxides |
| CN102659099A (en) * | 2012-05-29 | 2012-09-12 | 上海第二工业大学 | Preparation method of anisotropic graphene foam |
| CN106629679A (en) * | 2016-12-13 | 2017-05-10 | 北京圣盟科技有限公司 | Mass production technique of graphene |
-
2017
- 2017-06-15 CN CN201710461328.7A patent/CN107032337A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941694A (en) * | 2010-09-07 | 2011-01-12 | 湘潭大学 | Preparation method of high-dispersivity graphene |
| CN102173414A (en) * | 2011-03-18 | 2011-09-07 | 中国地质大学（武汉） | Method for preparing graphene oxide by chemical peeling |
| CN102502611A (en) * | 2011-11-15 | 2012-06-20 | 东南大学 | Method for rapidly preparing graphene in large quantities by utilizing graphite oxides |
| CN102491318A (en) * | 2011-12-13 | 2012-06-13 | 河北工业大学 | Method for preparing graphene oxide |
| CN102659099A (en) * | 2012-05-29 | 2012-09-12 | 上海第二工业大学 | Preparation method of anisotropic graphene foam |
| CN106629679A (en) * | 2016-12-13 | 2017-05-10 | 北京圣盟科技有限公司 | Mass production technique of graphene |
Non-Patent Citations (5)
| Title |
|---|
| 任小孟等: "Hummers法合成石墨烯的关键工艺及反应机理", 《材料工程》 * |
| 傅玲等: "Hummers法制备氧化石墨时影响氧化程度的工艺因素研究", 《炭素》 * |
| 王露: "改进Hummers法制备氧化石墨烯及其表征", 《包装学报》 * |
| 贾瑛等: "《轻质碳材料的应用》", 30 November 2013, 国防工业出版社 * |
| 邹正光等: "超声辅助Hummers 法制备氧化石墨烯", 《无机化学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892043A (en) * | 2020-08-06 | 2020-11-06 | 昆明理工大学 | Method for preparing reduced graphene oxide by one-pot method |
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Application publication date: 20170811 |