CN106082180A - A kind of acid intercalated graphite and Ammonium persulfate. are the method that raw material manufactures Graphene - Google Patents
A kind of acid intercalated graphite and Ammonium persulfate. are the method that raw material manufactures Graphene Download PDFInfo
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- CN106082180A CN106082180A CN201610392613.3A CN201610392613A CN106082180A CN 106082180 A CN106082180 A CN 106082180A CN 201610392613 A CN201610392613 A CN 201610392613A CN 106082180 A CN106082180 A CN 106082180A
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- graphene
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- graphite powder
- intercalated graphite
- ammonium persulfate
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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
- C01B2204/02—Single layer graphene
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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
- C01B2204/04—Specific amount of layers or specific thickness
Abstract
The invention discloses a kind of acid intercalated graphite and Ammonium persulfate. is the method that raw material manufactures Graphene, concrete technology is as follows: acid intercalated graphite powder, concentrated sulphuric acid and Ammonium persulfate. is stirred and makes mixed solution, at room temperature standing and reacting is after 1 50 days, is leached by acid intercalated graphite powder；The sour intercalated graphite powder leached is inserted the stripping carrying out Graphene in ultrasonic detacher or high shear detacher, obtains the Graphene of hygrometric state after centrifugation, finally by the Graphene lyophilization of hygrometric state, obtain powdered graphite alkene；The addition of concentrated sulphuric acid and Ammonium persulfate. is respectively 1 100 times and 1 50 times of acid intercalated graphite opaque amount.Using the form the few-layer graphene alkene that Graphene is single-layer graphene and the number of plies≤5 layer that the present invention is produced, these Graphenes still retain the intrinsic physicochemical property of raw graphite, and molecular structure is complete, do not have graphene oxide composition, belong to high-quality Graphene.
Description
Technical field
Present invention relates particularly to a kind of acid intercalated graphite and Ammonium persulfate. is the method that raw material manufactures Graphene, belong to novel
Material with carbon element manufacturing technology field.
Background technology
Graphene is the former molecular new carbon of monolayer carbon.Its electric conductivity is higher 10 times than copper, and hardness exceedes iron and steel
100 times, having the strongest tensile strength and heat conductivility, light transmittance reaches more than 82%.Graphene is at the integrated electricity of semiconductor electronic
Road, novel alloy and field of compound material will be widely used.Graphene has become the focus of whole world research.
Traditional Graphene manufacture method is to be pulverized by crystalline flake graphite, adds concentrated sulphuric acid, perchloric acid, concentrated nitric acid, glacial acetic acid
Carry out intercalation, oxidation with potassium permanganate, hydrogen peroxide, sodium nitrate etc., after high-temperature heat treatment, obtain graphite oxide by ultrasonic stripping method
Alkene, then with reducing agents such as hydrazine hydrate, potassium borohydride, sodium borohydrides, graphene oxide is reduced to Graphene.By initial oxidation stone
Ink prepare graphene oxide again with reducing agent reduction method produce Graphene have the biggest fault of construction, its functional parameter with
The intrinsic property of Graphene is too wide in the gap.And these techniques there is also flow process complexity, seriously polluted, it is difficult to industrial mass
The shortcoming produced.
Summary of the invention
It is an object of the invention to provide a kind of acid intercalated graphite and Ammonium persulfate. be the method that raw material manufactures Graphene,
Using Graphene prepared by the method still to retain the intrinsic physicochemical property of raw graphite, the method specifically uses following technique:
Acid intercalated graphite powder, concentrated sulphuric acid and Ammonium persulfate. are stirred and make mixed solution, at room temperature standing and reacting
After 1-50 days, acid intercalated graphite powder is leached；The sour intercalated graphite powder leached is inserted ultrasonic detacher or high shear detacher
In carry out the stripping of Graphene, obtain the Graphene of hygrometric state after centrifugation, finally by the Graphene lyophilization of hygrometric state, obtain
Powdered graphite alkene；The addition of concentrated sulphuric acid and Ammonium persulfate. is respectively 1-100 times and 1-50 times of acid intercalated graphite opaque amount.Excellent
The addition of selection of land, concentrated sulphuric acid and Ammonium persulfate. is respectively 20-40 times and 5-20 times of acid intercalated graphite opaque amount.
The present invention, with acid intercalated graphite powder as raw material, adds concentrated sulphuric acid and Ammonium persulfate. carries out intercalation again, then
Peel off Graphene by ultrasonic stripping method or high shear stripping method, then peel off Graphene by ultrasonic stripping method or high shear stripping method,
Charge stripping efficiency is greatly improved than traditional method.Use the Graphene that produced of the present invention be single-layer graphene and the number of plies≤
The form the few-layer graphene alkene of 5 layers, these Graphenes still retain the intrinsic physicochemical property of raw graphite, and molecular structure is complete, not oxidation
Graphene composition, belongs to high-quality Graphene.
When using the present invention to prepare Graphene, with acid intercalated graphite powder as raw material, enter at addition concentrated sulphuric acid and Ammonium persulfate.
After row intercalation again, the spacing of graphite linings expands 5-100 times.Concrete principle is probably, at the synergism of sulphuric acid
Under, Ammonium persulfate. is inserted into graphite layers, and reacts with the intercalation compound in raw material, produces a large amount of gas, on the top of gas
Lift lower graphite layers to expand away from slow, make the Van der Waals force of interlayer weaken or eliminate；Additionally the reacted product of Ammonium persulfate. in
Cation state, positively charged, and in the crystalline graphite powder of sulfur acid intercalation, graphite layers also with positive charge, identical
The interlamellar spacing producing electrostatic repulsion, beneficially graphite linings between positive charge expands further.
During preparing Graphene, sulphuric acid used may be recovered after filtering.
Specifically, described acid intercalated graphite powder uses following technique to make, by the crystalline graphite powder of 25-200 micron, dense sulfur
Acid, concentrated nitric acid and hydrogen peroxide mixing, stir after 0.5-1 hour at 30 DEG C, be warmed up to 40-50 DEG C, and constant temperature 12-24 hour
After, crystalline graphite powder is leached and washes after pH value is 7, be dried to obtain acid intercalated graphite powder.Preferably, concentrated sulphuric acid, dense nitre
The quality of acid and hydrogen peroxide is respectively 20-40 times of crystalline graphite powder quality, 5-20 times and 4-10 times.Crystalline graphite powder is filtered
Go out and wash after pH value is 7, being preferably dried at 60 DEG C, then obtain acid intercalated graphite powder.Crystalline graphite powder contains
Carbon amounts is >=99 mass %.
Using in the sour intercalated graphite powder that above-mentioned technique makes, the spacing of graphite linings is expanded fully, more added with
It is beneficial to use sulphuric acid and Ammonium persulfate. to carry out secondary intercalation, to prepare Graphene.
Detailed description of the invention
Embodiment 1
Take the particle diameter of the phosphorus content >=99 mass % crystalline graphite powder 1kg between 25-100 micron, concentrated sulphuric acid 30kg, dense
Nitric acid 5kg and hydrogen peroxide 4kg mixing, is kept stirring for, 30 DEG C of isothermal reactions 40 minutes, is then warmed up to 45 DEG C, continues perseverance
Temperature reaction was filtered after 12 hours, then the crystalline graphite powder that obtain is washed after pH value is 7 after filtering, and dries at 60 DEG C
Dry, obtain sour intercalated graphite powder.Obtain filtrate after filtration to reclaim.
Take above-mentioned acid intercalated graphite powder 0.5kg, concentrated sulphuric acid 10kg and the Ammonium persulfate. 2.5kg mixing obtained by the present embodiment
Use electromagnetic agitation 5 minutes afterwards, stop stirring, at room temperature filter after standing and reacting 1-7 days, the sour intercalation stone after filtering
Powdered ink is washed.After washing, acid intercalated graphite powder is inserted the stripping carrying out Graphene in ultrasonic detacher, after having peeled off
Use centrifuge to isolate the form the few-layer graphene alkene of single-layer graphene and the number of plies≤5 layer, finally carry out lyophilization and obtain high-performance
Graphite dilute.
Embodiment 2
Take the particle diameter of the phosphorus content >=99 mass % crystalline graphite powder 1kg between 100-200 micron, add concentrated sulphuric acid
20kg, concentrated nitric acid 10kg, hydrogen peroxide 6kg, be stirred by electromagnetic agitation, at 30 DEG C after isothermal reaction 1h, is warmed up to 40
DEG C, filter after continuation constant temperature 24h, then the crystalline graphite powder that will obtain after filtering is washed so that it is after pH value is 7, enter
Row centrifuge dehydration, is finally dried 48h at 60 DEG C, obtains sour intercalated graphite powder.The filtrate obtained after filtration is reclaimed.
After taking above-mentioned acid intercalated graphite powder 0.5kg, concentrated sulphuric acid 20kg and the Ammonium persulfate. 5kg mixing obtained by the present embodiment
By electromagnetic agitation 5 minutes, stop stirring, at room temperature filter after standing and reacting 7-15 days, the sour intercalation stone after filtering
Powdered ink is washed, and after washing, acid intercalated graphite powder is inserted the stripping carrying out Graphene in ultrasonic detacher, after having peeled off
Use centrifuge to isolate the form the few-layer graphene alkene of single-layer graphene and the number of plies≤5 layer, finally carry out lyophilization and obtain high-performance
Graphite dilute.
Embodiment 3
Take the particle diameter of the phosphorus content >=99 mass % crystalline graphite powder 1kg between 80-120 micron, add concentrated sulphuric acid
40kg, concentrated nitric acid 20kg, hydrogen peroxide 10kg, be kept stirring for, and 30 DEG C of isothermal reactions 30 minutes, is then warmed up to 50 DEG C, continues
Filter after continuing constant temperature 20h, then the crystalline graphite powder that will obtain after filtering is washed so that it is after pH value is 7, be centrifuged
Dehydration, is finally dried 30h at 60 DEG C, obtains sour intercalated graphite powder.The filtrate obtained after filtration is reclaimed.
Take above-mentioned acid intercalated graphite powder 0.5kg, concentrated sulphuric acid 15kg and the Ammonium persulfate. 10kg mixing obtained by the present embodiment
Use electromagnetic agitation 5 minutes afterwards, stop stirring, at room temperature filter after standing and reacting 45-50 days, the sour intercalation after filtering
Graphite powder is washed, and after washing, acid intercalated graphite powder is inserted the stripping carrying out Graphene in ultrasonic detacher, and stripping completes
The form the few-layer graphene alkene of single-layer graphene and the number of plies≤5 layer isolated by rear employing centrifuge, finally carries out lyophilization and obtains high property
The graphite of energy is dilute.
Claims (6)
1. one kind is the method that raw material manufactures Graphene by acid intercalated graphite and Ammonium persulfate., it is characterised in that use following work
Skill:
Acid intercalated graphite powder, concentrated sulphuric acid and Ammonium persulfate. are stirred and make mixed solution, at room temperature standing and reacting 1-50
After it, acid intercalated graphite powder is leached；Insert in ultrasonic detacher or high shear detacher by the sour intercalated graphite powder leached
The stripping of row Graphene, obtains the Graphene of hygrometric state, finally by the Graphene lyophilization of hygrometric state, obtains powdery after centrifugation
Graphene；
The addition of concentrated sulphuric acid and Ammonium persulfate. is respectively 1-100 times and 1-50 times of acid intercalated graphite opaque amount.
Method the most according to claim 1, it is characterised in that the addition of concentrated sulphuric acid and Ammonium persulfate. is respectively acid intercalation
20-40 times of graphite powder quality and 5-20 times.
Method the most according to claim 1, it is characterised in that described acid intercalated graphite powder uses following technique to make,
The crystalline graphite powder of 25-200 micron, concentrated sulphuric acid, concentrated nitric acid and hydrogen peroxide are mixed, at 30 DEG C, stirs 0.5-1 little
Shi Hou, is warmed up to 40-50 DEG C, and constant temperature is after 12-24 hour, is leached by crystalline graphite powder and washes after pH value is 7, be dried
To acid intercalated graphite powder.
Method the most according to claim 3, it is characterised in that the quality of concentrated sulphuric acid, concentrated nitric acid and hydrogen peroxide is respectively
20-40 times of crystalline graphite powder quality, 5-20 times and 4-10 times.
Method the most according to claim 3, it is characterised in that crystalline graphite powder is leached and washes after pH value is 7,
It is dried at 60 DEG C, then obtains acid intercalated graphite powder.
Method the most according to claim 3, it is characterised in that in crystalline graphite powder, phosphorus content is >=99 mass %.
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Cited By (3)
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| CN106564893A (en) * | 2016-11-10 | 2017-04-19 | 电子科技大学 | Hundred micron-order graphene oxide and preparation method thereof |
| CN109319767A (en) * | 2018-10-26 | 2019-02-12 | 天津大学 | A kind of graphene of preparation method and this method preparation of graphene |
| CN109761227A (en) * | 2019-02-24 | 2019-05-17 | 黎剑辉 | A method of being prepared on a large scale high-quality graphene |
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| CN109319767A (en) * | 2018-10-26 | 2019-02-12 | 天津大学 | A kind of graphene of preparation method and this method preparation of graphene |
| CN109761227A (en) * | 2019-02-24 | 2019-05-17 | 黎剑辉 | A method of being prepared on a large scale high-quality graphene |
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Application publication date: 20161109 |