CN106564886A - Method for preparing graphene through dry grinding and stripping - Google Patents
Method for preparing graphene through dry grinding and stripping Download PDFInfo
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- CN106564886A CN106564886A CN201610914000.1A CN201610914000A CN106564886A CN 106564886 A CN106564886 A CN 106564886A CN 201610914000 A CN201610914000 A CN 201610914000A CN 106564886 A CN106564886 A CN 106564886A
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- graphite
- graphene
- dry state
- prepares graphene
- state grinding
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention provides a method for preparing graphene through dry grinding and stripping. According to the method for preparing the graphene through dry grinding and stripping, dense crystallized graphite, flake graphite and cryptocrystalline graphite are mixed according to a certain ratio; and because the dense crystallized graphite, the flake graphite and the cryptocrystalline graphite have different kinds of lubricity, hardness and plasticity, under the condition that polydimethylsiloxane is used as an assistant, graphite is rapidly stripped through dry direct grinding due to the different performances of the different kinds of graphite, and the stripping performance is high. Besides, through the dispersion lubricating feature of the polydimethylsiloxane, the structure of the obtained graphene layer is well preserved, and the grinding device can be a Raymond mill or a vertical mill or a ball mill.
Description
Technical field
The present invention relates to grapheme material field, and in particular to the method ground by dry state prepares highly purified graphite
Alkene material, more particularly to using the different physical and chemical performances of different graphite types solving stone occur in dry state method preparation process
The problem of black alkene hard aggregation.
Background technology
Graphene has very excellent property, such as electronic property, power due to itself distinctive structure at many aspects
Property, mechanical performance, optical property, thermal property etc. are learned, it is referred to as the star of prospective material.Graphene is to send out in the world at present
Existing most thin material, thickness in monolayer only has 0.3354nm, but its specific surface area is up to 2965m2/g.Graphene is also current generation
Mechanical strength highest material in boundary, its elastic modelling quantity is up to 1TPa, and tensile strength is up to 180GPa, and fracture strength reaches
125GPa.Additionally, the room temperature pyroconductivity of monolayer deflocculated graphite alkene can reach 3000～5000W/ (mK), electrical conductivity is
2000S/cm.Therefore, Graphene has at aspects such as composite, energy storage, sensor, photoelectric material and catalyst carriers
It is widely applied prospect.
Preparing the method for Graphene at present mainly has physics to peel off and the big class of chemosynthesis two.Mechanical stripping is physics legal system
The important means of standby Graphene, mainly includes two kinds of wet method and dry method.At present during the preparation research of Graphene, great majority
People all by focus in wet method research, mainly make in a wet process by the patent for preparing Graphene with regard to mechanical stripping delivered
Based on standby.But wet method prepare Graphene there is a problem of it is certain：Wet method to be prepared needed during Graphene and helped using substantial amounts of
Agent, the purity for easily causing Graphene is relatively low；Because intergranular relative collision probability reduces in wet method preparation process, lead
Cause charge stripping efficiency relatively low；Need to use chemical drugss and solvent in a large number in wet method preparation process, easily pollute environment；Adopt
To be prepared needed after Graphene with wet method and be dried process, process is complicated, and energy consumption is larger, high cost.Dry state method prepares graphite
Alkene is not present in the problems referred to above, but preparation process, due to being disperseed without solution and dispersant, easily makes in preparation process
Into reunion, cause the Graphene poor-performing for preparing.There is partial monopoly to have studied dry state method at present and prepare Graphene.
Chinese patent patent application number 201410515440.0 proposes a kind of graphene nanometer sheet and preparation method thereof, should
Mainly after by graphite and solid high-polymer mixed grinding, Jing high-temperature heat treatments are disperseed high polymer for invention
The preferable graphene nanometer sheet of property.
Chinese patent patent application number 201310641974.3 proposes a kind of preparation side of polymer-graphite alkene mixture
Method, the invention is mainly first by the way that graphite is soaked in the solvent for being dissolved with high polymer, and high polymer-graphite mixing is obtained
Thing, is then ground to high polymer-graphite mixture, obtains polymer-graphite alkene mixture.
Chinese patent patent application number 201210202629.5 proposes the preparation side of a kind of Graphene or graphene oxide
Method, the invention adopts magnetic draw point for abrasive body, and outside plastics, ceramics, macromolecular material, austenite stainless steel container one is applied
Variation magnetic field, to graphite dry state grinding is carried out.
Chinese patent patent application number 201010179119.1 proposes a kind of high-efficiency and low-cost mechanical stripping and prepares stone
The method of black alkene or graphene oxide, the invention is mainly by adding other particulate matters during mechanical stripping, to promote
Intergranular mutual collision, improves mechanical stripping efficiency.
The present invention is carried out mixing and is ground using the physical chemical differences between different graphite types with different types of graphite
Mill, to reduce the mutual reunion between graphene particles, obtain dispersibility compared with Graphene.And add in process of lapping poly-
Dimethyl siloxane is protected to graphene-structured, and further promotes the dispersion of Graphene.
The content of the invention
For the problem for being susceptible to reunite present in current dry process Graphene process, and introduce excessive magazine
Defect, the present invention using physical chemical differences such as hardness, plasticity, the lubricities between different graphite types, by densification
Crystalloid graphite, crystalline flake graphite, aphanitic graphite press different quality than mixed grinding, and poly- diformazan is added during grinding
Radical siloxane further promotes the dispersion of Graphene, adopts the following technical scheme that：
Close crystalloid graphite, crystalline flake graphite, aphanitic graphite are weighed by certain mass ratio, immersion 0- is carried out in acid solution
2h, then filters in graphite, and deionized water carries out cleaning 3-5 time, and the graphite after cleaning is dried at 90 DEG C；
A certain amount of polydimethylsiloxane is weighed in proportion to be dissolved in solvent, then different types of graphite is pressed into one
Certainty ratio mixing is poured in solution, soaks 1-3h, is filtered, is dried, and obtains graphite-polydimethylsiloxanemixture mixture；
Graphite-polydimethylsiloxanemixture mixture is peeled off in mechanical stripping equipment, is then carried out to peeling off product
Sieve process, obtain the Graphene of size uniformity.
Preferably, the compact crystal shape graphite-structure is fine and close, and hardness is 3-5, and plasticity and lubricity are poor.
Preferably, the crystalline flake graphite short texture, hardness is 1-2, and plasticity and lubricity are preferable.
Preferably described aphanitic graphite consistency, plasticity, lubricity are between compact crystal shape graphite and crystalline flake graphite
Between, hardness is 2-3.
Preferably, described solvent is butyl acetate, diethyl carbonate, DBE, toluene, Ethyl methyl carbonate, isopropanol, fourth
Base cellosolve acetate, Allyl carbonate, DMSO, dimethyl succinate, NMP, dimethylbenzene, dibutyl phthalate, carbonic acid
The combination of any one or more in dimethyl ester and diphenyl carbonate.
Preferably, the mass ratio of the compact crystal shape graphite, crystalline flake graphite and aphanitic graphite is 3：1：1.
Preferably, the mass ratio of the compact crystal shape graphite, crystalline flake graphite and aphanitic graphite be, 1：3：1.
Preferably, the consumption of described polydimethylsiloxane is the 10-20% of admixed graphite gross mass.
Preferably, the milling apparatus select the one kind in Raymond mill, vertical mill, ball mill, astrolabe mill.
Preferably, described grinding rotating speed is 500-2000rpm/min, and milling time is 0-100h.
Preferably, described abrasive product needs to carry out process of sieving through 500 mesh copper mesh.
The method that a kind of present invention dry state grinding stripping prepares Graphene, compared with prior art, the characteristics of its protrusion and
Excellent effect is：
1. the present invention proposes a kind of method for preparing Graphene using different type graphite mixed grinding under dry conditions,
The creative characteristic different using different graphite hardness, realizes the stripping of graphite piece self-grind.
2. compared with wet method prepares Graphene, this method has introducing that is more easy, reducing abrasive media, dirty without environment
The advantages of dye, low cost, energy large-scale continuous production.
3. the Graphene purity that prepared by this method is high, and need not carry out subsequent treatment.
4. this method can both protect Graphene knot in process of lapping using polydimethylsiloxane as grinding aid
Structure is not destroyed, and can further promote the dispersion of Graphene, prevents from reuniting, and reduces the physical and chemical performance of Graphene.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as into the present invention
Scope be only limitted to Examples below.In the case of without departing from said method thought of the present invention, according to ordinary skill
Various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
Compact crystal shape graphite, natural flake graphite, three kinds of aphanitic graphite are chosen as graphite raw material, quality difference
For 60g, 20g, 20g, three kinds of graphite are poured in dilute hydrochloric acid and soaks 1h, then carry out sucking filtration, and deionized water cleaning 3-5
It is secondary, finally admixed graphite is put into in constant temperature oven the dry for standby at 90 DEG C；
10g polydimethylsiloxane is weighed, in being dissolved in 500ml xylene solvents, after it is completely dissolved, will be walked
SuddenlyIn admixed graphite pour into dissolved with polydimethylsiloxane xylene solution in soak 1h, then filtered, without the need for
Washing is directly placed in thermostatic drying chamber dries at 120 DEG C, obtains graphite-polydimethylsiloxanemixture mixture；
Graphite-polydimethylsiloxanemixture mixture is poured in ball mill, in the case where rotating speed is 500rpm 48h is ground, obtain stone
Black alkene product；
By stepIn graphene product carry out process of sieving with the copper mesh of 500 mesh, obtain the graphite that size is about 30 μm
Alkene product.
Embodiment 2
Compact crystal shape graphite, natural flake graphite, three kinds of aphanitic graphite are chosen as graphite raw material, quality difference
For 20g, 60g, 20g, three kinds of graphite are poured in dilute hydrochloric acid and soaks 1h, then carry out sucking filtration, and deionized water cleaning 3-5
It is secondary, finally admixed graphite is put into in constant temperature oven the dry for standby at 90 DEG C；
10g polydimethylsiloxane is weighed, in being dissolved in 500ml xylene solvents, after it is completely dissolved, will be walked
SuddenlyIn admixed graphite pour into dissolved with polydimethylsiloxane xylene solution in soak 1h, then filtered, without the need for
Washing is directly placed in thermostatic drying chamber dries at 120 DEG C, obtains graphite-polydimethylsiloxanemixture mixture；
Graphite-polydimethylsiloxanemixture mixture is poured in ball mill, in the case where rotating speed is 500rpm 48h is ground, obtain stone
Black alkene product；
By stepIn graphene product carry out process of sieving with the copper mesh of 500 mesh, obtain the graphite that size is about 60 μm
Alkene product.
Embodiment 3
Compact crystal shape graphite, natural flake graphite, three kinds of aphanitic graphite are chosen as graphite raw material, quality difference
For 20g, 20g, 60g, three kinds of graphite are poured in dilute hydrochloric acid and soaks 1h, then carry out sucking filtration, and deionized water cleaning 3-5
It is secondary, finally admixed graphite is put into in constant temperature oven the dry for standby at 90 DEG C；
10g polydimethylsiloxane is weighed, in being dissolved in 500ml xylene solvents, after it is completely dissolved, will be walked
SuddenlyIn admixed graphite pour into dissolved with polydimethylsiloxane xylene solution in soak 1h, then filtered, without the need for
Washing is directly placed in thermostatic drying chamber dries at 120 DEG C, obtains graphite-polydimethylsiloxanemixture mixture；
Graphite-polydimethylsiloxanemixture mixture is poured in ball mill, in the case where rotating speed is 500rpm 48h is ground, obtain stone
Black alkene product；
By stepIn graphene product carry out process of sieving with the copper mesh of 500 mesh, obtain the graphite that size is about 50 μm
Alkene product.
Embodiment 4
Compact crystal shape graphite, natural flake graphite, three kinds of aphanitic graphite are chosen as graphite raw material, quality difference
For 30g, 30g, 30g, three kinds of graphite are poured in dilute hydrochloric acid and soaks 1h, then carry out sucking filtration, and deionized water cleaning 3-5
It is secondary, finally admixed graphite is put into in constant temperature oven the dry for standby at 90 DEG C；
18g polydimethylsiloxane is weighed, in being dissolved in 500ml xylene solvents, after it is completely dissolved, will be walked
SuddenlyIn admixed graphite pour into dissolved with polydimethylsiloxane xylene solution in soak 1h, then filtered, without the need for
Washing is directly placed in thermostatic drying chamber dries at 120 DEG C, obtains graphite-polydimethylsiloxanemixture mixture；
Graphite-polydimethylsiloxanemixture mixture is poured in ball mill, in the case where rotating speed is 500rpm 48h is ground, obtain stone
Black alkene product；
By stepIn graphene product carry out process of sieving with the copper mesh of 500 mesh, obtain the graphite that size is about 50 μm
Alkene product.
Embodiment 5
Compact crystal shape graphite, natural flake graphite, three kinds of aphanitic graphite are chosen as graphite raw material, quality difference
For 50g, 30g, 20g, three kinds of graphite are poured in dilute hydrochloric acid and soaks 1h, then carry out sucking filtration, and deionized water cleaning 3-5
It is secondary, finally admixed graphite is put into in constant temperature oven the dry for standby at 90 DEG C；
10g polydimethylsiloxane is weighed, in being dissolved in 500ml xylene solvents, after it is completely dissolved, will be walked
SuddenlyIn admixed graphite pour into dissolved with polydimethylsiloxane xylene solution in soak 1h, then filtered, without the need for
Washing is directly placed in thermostatic drying chamber dries at 120 DEG C, obtains graphite-polydimethylsiloxanemixture mixture；
Graphite-polydimethylsiloxanemixture mixture is poured in ball mill, in the case where rotating speed is 500rpm 48h is ground, obtain stone
Black alkene product；
By stepIn graphene product carry out process of sieving with the copper mesh of 500 mesh, obtain the graphite that size is about 40 μm
Alkene product.
Embodiment 6
Compact crystal shape graphite, natural flake graphite, three kinds of aphanitic graphite are chosen as graphite raw material, quality difference
For 50g, 30g, 20g, three kinds of graphite are poured in dilute hydrochloric acid and soaks 1h, then carry out sucking filtration, and deionized water cleaning 3-5
It is secondary, finally admixed graphite is put into in constant temperature oven the dry for standby at 90 DEG C；
20g polydimethylsiloxane is weighed, in being dissolved in 500ml xylene solvents, after it is completely dissolved, will be walked
SuddenlyIn admixed graphite pour into dissolved with polydimethylsiloxane xylene solution in soak 1h, then filtered, without the need for
Washing is directly placed in thermostatic drying chamber dries at 120 DEG C, obtains graphite-polydimethylsiloxanemixture mixture；
Graphite-polydimethylsiloxanemixture mixture is poured in ball mill, in the case where rotating speed is 500rpm 48h is ground, obtain stone
Black alkene product；
By stepIn graphene product carry out process of sieving with the copper mesh of 500 mesh, obtain the graphite that size is about 40 μm
Alkene product.
Claims (9)
1. the method that a kind of dry state grinding stripping prepares Graphene, it is characterised in that using the lubricity of different graphite, hardness, can
Plasticity physical chemical differences, certain mass is pressed than mixed grinding system by close crystalloid graphite, crystalline flake graphite, aphanitic graphite
Standby Graphene, concrete grammar is as follows：
Close crystalloid graphite, crystalline flake graphite, aphanitic graphite are weighed by certain mass ratio, immersion 0- is carried out in acid solution
2h, then filters in graphite, and deionized water carries out cleaning 3-5 time, and the graphite after cleaning is dried at 90 DEG C；
Weigh a certain amount of polydimethylsiloxane in proportion to be dissolved in solvent, then by step（1）Dry inhomogeneity
The graphite mixing of type is poured in solution, soaks 1-3h, is filtered, is dried, and obtains graphite-polydimethylsiloxanemixture mixture；
Graphite-polydimethylsiloxanemixture mixture is peeled off in mechanical stripping equipment, is then carried out to peeling off product
Sieve process, obtain the Graphene of size uniformity.
2. a kind of method that according to claim 1 dry state grinding stripping prepares Graphene, it is characterised in that the fine and close knot
Crystalline graphite-structure is fine and close, and hardness is 3-5.
3. a kind of method that according to claim 1 dry state grinding stripping prepares Graphene, it is characterised in that the scale stone
Ink structure is loose, and hardness is 1-2.
4. a kind of method that according to claim 1 dry state grinding stripping prepares Graphene, it is characterised in that the cryptocrystalline
Graphite, hardness is 2-3.
5. a kind of method that according to claim 1 dry state grinding stripping prepares Graphene, it is characterised in that the fine and close knot
The mass ratio of crystalline graphite, crystalline flake graphite and aphanitic graphite is 3：1：1.
6. a kind of method that according to claim 1 dry state grinding stripping prepares Graphene, it is characterised in that the fine and close knot
The mass ratio of crystalline graphite, crystalline flake graphite and aphanitic graphite is 1：3：1.
7. a kind of method that according to claim 1 dry state grinding stripping prepares Graphene, it is characterised in that described poly- two
The consumption of methylsiloxane is the 10-20% of admixed graphite gross mass.
8. a kind of method that according to claim 1 dry state grinding stripping prepares Graphene, it is characterised in that described solvent
For butyl acetate, diethyl carbonate, DBE, toluene, Ethyl methyl carbonate, isopropanol, butyl cellosolve acetate, Allyl carbonate,
It is arbitrary in DMSO, dimethyl succinate, NMP, dimethylbenzene, dibutyl phthalate, dimethyl carbonate and diphenyl carbonate
Plant or two or more combinations.
9. a kind of method that according to claim 1 dry state grinding stripping prepares Graphene, it is characterised in that the grinding sets
One kind in alternative Raymond mill, vertical mill, ball mill, astrolabe mill.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107523058A (en) * | 2017-09-25 | 2017-12-29 | 多凌新材料科技股份有限公司 | A kind of method for preparing graphene/silicon glue composite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724869A (en) * | 2013-12-03 | 2014-04-16 | 华侨大学 | Preparation method for mixture of polymer and graphene |
| CN106006624A (en) * | 2016-07-01 | 2016-10-12 | 成都新柯力化工科技有限公司 | Preparation method of graphene material by dry air flow stripping and graphene material |
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- 2016-10-20 CN CN201610914000.1A patent/CN106564886B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724869A (en) * | 2013-12-03 | 2014-04-16 | 华侨大学 | Preparation method for mixture of polymer and graphene |
| CN106006624A (en) * | 2016-07-01 | 2016-10-12 | 成都新柯力化工科技有限公司 | Preparation method of graphene material by dry air flow stripping and graphene material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107523058A (en) * | 2017-09-25 | 2017-12-29 | 多凌新材料科技股份有限公司 | A kind of method for preparing graphene/silicon glue composite |
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