CN107879332A - The method that space-time synchronous ultrasound ball-milling method peels off preparing graphite alkene - Google Patents
The method that space-time synchronous ultrasound ball-milling method peels off preparing graphite alkene Download PDFInfo
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Abstract
The invention discloses a kind of method that space-time synchronous ultrasound ball-milling method peels off preparing graphite alkene, comprise the following steps：Graphite raw material is added in ultrasonic ball-grinding machine with peeling off reagent, 2~96h of ball milling under ultrasonic environment, mixture is by separating, washing, being dried to obtain graphene powder.This method peels off graphite using space-time synchronous ultrasound and ball-milling method, by ball milling Strong shear power while the two synergistic function makes graphite layers expansion in situ.This method has the advantages of high efficiency, high yield, suitable for preparing graphene in batches.
Description
Technical field
The present invention relates to a kind of graphene preparation method, particularly relates to a kind of space-time synchronous ultrasound ball-milling method and peels off graphite system
The method of standby graphene.
Background technology
The two-dimensional material that graphene is made up of single layer of carbon atom.Graphene is since being found, due to its peculiar property
Matter is paid close attention to by numerous researchers, and wide application prospect is demonstrated out in fields such as new energy, new materials.
Batch graphene preparation method is broadly divided into chemistry redox method, physics stripping method and chemical vapor deposition at present
Method.Chemistry redox method has easily a large amount of the advantages of preparing, but also has simultaneously and produce lacking for a large amount of spent acid and heavy metal pollution
Fall into.Although chemical vapour deposition technique can prepare graphene film and a small amount of powder in batches, the harsh conditions such as high temperature are needed,
Prepared graphene is mostly film morphology simultaneously, is unfavorable for doing filler additive.Comparatively, physics stripping method has scale
Change prepares the potentiality of graphene.Physics stripping method is mainly that the Van der Waals force of graphite layers is overcome using mechanical external force, is allowed to certainly
It is upper and under stripping into graphene nanometer sheet.
Ultrasonic stripping method is to be weakened using the cavitation of ultrasonic wave and overcome the Van der Waals'attractive force between graphene layer,
Cause micro-nano foam to increase in particular by ultrasonic wave shells graphene with rupture generation intense impact and pressure oscillation
From with disperseing.1-METHYLPYRROLIDONE is the relatively early solvent for being used for ultrasound and peeling off graphene, and this method can obtain 0.01mg/mL
Graphene dispersing solution (Adv Funct Mater, 2009,19,3680).O-dichlorohenzene peels off graphene used also as ultrasound
Reagent, 0.03mg/mL dispersion liquid (Nano Lett, 2009,9,3460) can be obtained.Supercritical ultrasonics technology peels off graphite and prepares stone
Black alkene is simple and easy, but the graphene dispersion concentration that this method obtains is very low, generally less than 0.01mg/mL, and produces
Peeling force it is weaker, charge stripping efficiency is relatively low.
General milling method is also to prepare one of method of graphene, and this method is mutually hit using ball-milling medium produces with rolling
Strong shearing force is given birth to peel off graphite.Chinese invention patent CN103570005A mixes graphite and sodium sulphate etc., Ran Hougao
Fast ball milling 8~12 hours, then purifying obtain graphene powder.Patent of invention CN105883773A by graphite and benzene sulfonic acid sodium salt,
Cyclopentadiene, sand milling agent etc. are mixed together, and 2000rpm ball millings 4~48 hours, graphene powder are obtained through what is isolated and purified.Ball
Mill method plant maintenance can prepare graphene with easy to operate with larger amount of, but this method preparation time is grown, graphene
Yield is still relatively low.
In summary, mechanical stripping method prepares graphene and the shortcomings that low yield, preparation efficiency is low, Er Qiexian also be present at present
Have in technology and still under same space-time while not act on graphite progress graphene using ultrasonic power and ball milling method simultaneously
The method of stripping, this method ultrasound and ball milling Synergistic release effect simultaneously, while making graphite layers expansion in situ by
Ball milling Strong shear power, charge stripping efficiency greatly promote, and suitable batch prepares graphene.
The content of the invention
It is an object of the invention to provide a kind of efficient space-time synchronous ultrasound ball-milling method to peel off preparing graphite alkene
Method.
To achieve the above object, space-time synchronous ultrasound ball-milling method provided by the present invention peels off the side of preparing graphite alkene
Method, comprise the following steps：Graphite raw material is added in ultrasonic ball-grinding machine with peeling off reagent, the ball milling under ultrasonic environment,
Ball-milling Time is preferably 2~96h, and mixture is by separating, being dried to obtain graphene powder.
Alternatively, the stripping reagent is organic solvent, and the organic solvent includes 1-METHYLPYRROLIDONE, N, N- diformazans
Base formamide, DMAC N,N' dimethyl acetamide, isopropanol, acetone, ethanol, cyclohexanone, chloroform, fluorine-containing aromatic hydrocarbons, octafluoro toluene, hexafluoro
Benzene, phenyl-pentafluoride cyanogen, five fluoropyrimidines, chloroform, cyclopentanone, dimethyl sulfoxide (DMSO), tetrahydrofuran, gamma-butyrolacton, N- dodecyls
Pyrrolidones, NVP, 1,3- dimethyl-2-imidazolinones.
Alternatively, the reagent of peeling off is the surfactant-aqueous systems formed by surfactant and water configuration, described
Surfactant includes：Sodium taurocholate, NaTDC, taurine sodium taurocholate, 3- [(3- courages amido propyl) dimethylamino] are simultaneously
Acid inner salt, neopelex, dodecyl sodium sulfate, didodecyldimethylammbromide bromide, dodecyl malt
Sugar, polyvinylpyrrolidone, kayexalate, Myrj 45, PEO-PPOX-polycyclic
Oxidative ethane triblock copolymer, sorbitan monooleate APEO, Triton X-100, cellulose nanometer
It is brilliant.
Alternatively, the stripping reagent is conjugated structure molecular solvent, and the conjugated structure molecule includes：1- amino pyrene,
1- pyrenes methylamine hydrochloride, pyrene, benzylamine, 7,7,8,8- four cyano benzoquinones bismethane, 9- anthroic acids, 1- pyrenes butanol, 1- pyrene carboxylics
Acid, 1- pyrenes butyric acid, 1- pyrenes azochlorosulfonate acid hydrate, 1- pyrenes sodium sulfonate, 6,8- dihydroxy -1,3- pyrenes sulfonate, 8- hydroxyl pyrenes 1,3,6-
Trisulfonic acid sodium salt, 1,3,6,8- pyrenes sodium salt, N, N- dimethyl diaza pyrenes villaumite, coronene tetramethyl acid potassium salt.
Alternatively, the stripping reagent is ionic liquid, and the cation of the ionic liquid includes glyoxaline cation, pyridine
One or more in cation, quaternary ammonium salt cationic and quaternary phosphonium salt cation, the anion of the ionic liquid include tetrafluoro
One or more in borate anion, hexafluorophosphoric acid salt anionic, chlorion and bromide ion.
Alternatively, the reagent of peeling off is the ionic liquid-filler shear thickening formed by ionic liquid and filler configuration
System；Wherein, the cation of the ionic liquid includes glyoxaline cation, pyridylium, quaternary ammonium salt cationic and quaternary alkylphosphonium salt
One or more in cation, the anion of the ionic liquid include tetrafluoro boric acid salt anionic, hexafluorophosphate the moon from
One or more in son, chlorion and bromide ion；The filler includes silica, aluminum oxide, magnesia, zinc oxide, oxygen
Change the one or more in nickel, cupric oxide, beryllium oxide, carbon ball, polymer microballoon and CNT, the size of the filler is
1nm~100 μm.Shear thickening system refers to that system viscosity shows the increasing of 2~3 orders of magnitude with the increase of shear rate
Add.The program utilizes the shear thickening behavior of shear thickening system, and viscosity is significantly increased when in certain shear, favorably
In peeling off graphene from graphite raw material；And when high-rate of shear removes, mixing liquid viscosity declines to a great extent, and fluid is presented
State, be advantageous to the separation and collection of graphene.
Alternatively, the graphite raw material includes native graphite, artificial synthesized graphite, expanded graphite, fluorographite and oxygen
One or more in graphite.
Preferably, the ultrasonic power of the ultrasonic ball-grinding machine is 0.2~1000kW, 100~750rpm of rotating speed.
Beneficial effects of the present invention are：The present invention using ultrasound and ball milling same space-time Synergistic release effect come
Graphite is peeled off, i.e. Synergistic of the material again by ball milling Strong shear while by the ultrasonic cavitation of ultrasonic wave is made
With by ball milling Strong shear power while making graphite layers expansion in situ, being more easy to batch and prepare graphene.It is this synergy by
Ultrasonic wave acts on same spatio-temporal synergy synergy to the ultrasonic cavitation of graphite layers and the Strong shear of ball milling and produced.The party
Method technique is unique, and mild condition, cost is controllable, and suitable batch prepares graphene.
Brief description of the drawings
Fig. 1~3 are respectively the transmission electron microscope photo of graphene prepared by embodiment 1,3,5.
Embodiment
The method that space-time synchronous ultrasound ball-milling method provided by the present invention peels off preparing graphite alkene, its step are as follows：
Graphite raw material is added in ultrasonic ball-grinding machine with peeling off reagent, 2~96h of ball milling under ultrasonic environment, ultrasonic ball milling is set
Standby ultrasonic power is 0.2~1000kW, 100~750rpm of rotating speed.Mixture is by separating, washing, being dried to obtain graphene
Powder.The reagent of following several types can be used by peeling off reagent：
1) conventional organic stripping solvent, including 1-METHYLPYRROLIDONE, DMF, N, N- dimethylacetamides
Amine, isopropanol, acetone, ethanol, cyclohexanone, chloroform, fluorine-containing aromatic hydrocarbons, octafluoro toluene, phenyl-hexafluoride, phenyl-pentafluoride cyanogen, five fluoropyrimidines, three
Chloromethanes, cyclopentanone, dimethyl sulfoxide (DMSO), tetrahydrofuran, gamma-butyrolacton, N-dodecylpyrrolidone, N- ethenyl pyrrolidones
Ketone, 1,3- dimethyl-2-imidazolinones；
2) surfactant-aqueous systems formed by surfactant and water configuration, the surfactant include：Cholic acid
Sodium, NaTDC, taurine sodium taurocholate, 3- [(3- courages amido propyl) dimethylamino] and acid inner salt, detergent alkylate
It is sodium sulfonate, dodecyl sodium sulfate, didodecyldimethylammbromide bromide, n-dodecyl-β-D-maltoside, polyvinylpyrrolidone, poly-
SSS, Myrj 45, PEO-PPOX-PEO triblock copolymer, mistake
Water sorbitol monooleate APEO, Triton X-100, Cellulose nanocrystal；
3) conjugated structure molecular solvent, the conjugated structure molecule include：1- amino pyrene, 1- pyrenes methylamine hydrochloride, pyrene, benzyl
Amine, 7,7,8,8- four cyano benzoquinones bismethane, 9- anthroic acids, 1- pyrenes butanol, 1- pyrenes carboxylic acid, 1- pyrenes butyric acid, 1- pyrene sulfonic acid
Hydrate, 1- pyrenes sodium sulfonate, 6,8- dihydroxy -1,3- pyrenes sulfonate, 8- hydroxyl pyrene 1,3,6- trisulfonic acids sodium salt, 1,3,6,8- pyrenes
Sodium salt, N, N- dimethyl diaza pyrenes villaumite, coronene tetramethyl acid potassium salt.
4) ionic liquid, the ionic liquid are made up of cation and anion, wherein, cation include imidazoles sun from
Son, pyridylium, quaternary ammonium salt cationic or quaternary phosphonium salt cation, anion include tetrafluoro boric acid salt anionic, hexafluorophosphoric acid
Salt anionic, chlorion or bromide ion；
5) ionic liquid-filler shear thickening system, formed by above-mentioned ionic liquid and filler configuration, the filler includes
Silica, aluminum oxide, magnesia, zinc oxide, nickel oxide, cupric oxide, beryllium oxide, carbon ball, polymer microballoon and CNT
In one or more, the size of the filler is 1nm~100 μm.
Below by specific embodiment, the present invention is described in further detail.
Embodiment 1
5g graphite and 50mLN- methyl pyrrolidones are put into ultrasonic ball mill, ultrasonic power is controlled in 1.5kW, ball
After grinding rotating speed 500rpm, ultrasonic ball milling 2h, product is by separating, washing, being dried to obtain graphene powder.
Embodiment 2
5g graphite and 150mL DMFs are put into ultrasonic ball mill, ultrasonic power is controlled in 5kW,
After rotational speed of ball-mill 500rpm, ultrasonic ball milling 1h, product is by separating, washing, being dried to obtain graphene powder.
Embodiment 3
5g graphite and 50mL 1- butyl -3- methylimidazole hexafluorophosphates are put into ultrasonic ball mill, ultrasonic power
Control is after 2.5kW, rotational speed of ball-mill 500rpm, ultrasonic ball milling 3h, and product is by separating, washing, being dried to obtain graphene powder.
Embodiment 4
By 5g graphite and 5g PEOs-propyleneoxide-ethyleneoxide (P123) aqueous solution, 150mL water is put into ultrasound
In ball mill, ultrasonic power is controlled after 5kW, rotational speed of ball-mill 500rpm, ultrasonic ball milling 1h, and product is by separating, washing, dry
It is dry to obtain graphene powder.
Embodiment 5
By 5g graphite and 5g neopelexes, 150mL water is put into ultrasonic ball mill, and ultrasonic power control exists
After 5kW, rotational speed of ball-mill 500rpm, ultrasonic ball milling 1h, product is by separating, washing, being dried to obtain graphene powder.
Embodiment 6
The present embodiment uses ionic liquid-silica shear thickening system, is specially：Nano silicon 15g is taken, is added
Enter in 50mL 1- ethoxy -3- methyl imidazolium tetrafluoroborates, ultrasonic disperse 1h, add 5g graphite, ultrasonic power control exists
After 5kW, rotational speed of ball-mill 500rpm, ultrasonic ball milling 1h, product is by separating, washing, being dried to obtain graphene powder.
Reference examples 1
5g graphite and 50mL 1-METHYLPYRROLIDONEs are first put into 1.5kW in ordinary ultrasonic machine, are ultrasonically treated 2 hours, then
Ball milling 2h in ball mill is transferred to, rotating speed 500rpm, product is by separating, washing, being dried to obtain graphene powder.
Reference examples 2
5g graphite is transferred to ball milling 2h in ball mill with 50mL 1-METHYLPYRROLIDONEs, and rotating speed 500rpm, product is through undue
From, wash, be dried to obtain graphene powder.
Reference examples 3
5g graphite is transferred to ball milling 2h in ball mill with 50mL 1-METHYLPYRROLIDONEs, rotating speed 500rpm, is put into ordinary ultrasonic
1.5kW in machine, 2 hours products are ultrasonically treated by separating, washing, being dried to obtain graphene powder.
Interpretation of result
Dispersion liquid (before separation) concentration prepared by each embodiment, reference examples and graphene yield are detected, and with
Dispersion liquid concentration disclosed in document is contrasted, and the results are shown in Table 1.
Graphene yield and dispersion liquid concentration in 1 each embodiment of table, reference examples and document
As shown above, the graphene prepared by each embodiment, graphene dispersing solution concentration are 2.5~8.9mg/mL, stone
Less than five layers yield of black alkene are that the mass percent that less than five layers (containing 5 layers), graphene accounted for whole graphenes is 65~78%.And
In reference examples, graphene dispersing solution concentration is 0.11~0.16mg/mL, and less than five layers yield of graphene are 9~18%；With reference to text
Graphene dispersing solution concentration described in offering is 0.01~0.7mg/mL.Contrast understands, graphene dispersing solution concentration of the present invention, stone
Black alkene is far above reference examples and bibliography less than five layers of yield, is adapted to the scattered graphite of a large amount of preparation high concentrations, high stable
Alkene.
The transmission electron microscope photo for the graphite ene product that embodiment 1, embodiment 3, embodiment 5 are prepared is shown in respectively
Fig. 1, Fig. 2, Fig. 3.It can be seen that from photo：The graphite ene product that embodiment 1, embodiment 3, embodiment 5 are prepared it is saturating
It is all translucent, structural integrity to penetrate electron micrograph, and the number of plies is few.
Claims (9)
1. a kind of method that space-time synchronous ultrasound ball-milling method peels off preparing graphite alkene, it is characterised in that：Comprise the following steps：
Graphite raw material is added in ultrasonic ball-grinding machine with peeling off reagent, the ball milling under ultrasonic environment, mixture, which passes through, to be separated, be dry
It is dry to obtain graphene powder.
2. the method that space-time synchronous ultrasound ball-milling method according to claim 1 peels off preparing graphite alkene, its feature exist
In：The stripping reagent is organic solvent, and the organic solvent includes 1-METHYLPYRROLIDONE, DMF, N,
N- dimethyl acetamides, isopropanol, acetone, ethanol, cyclohexanone, chloroform, fluorine-containing aromatic hydrocarbons, octafluoro toluene, phenyl-hexafluoride, phenyl-pentafluoride
Cyanogen, five fluoropyrimidines, chloroform, cyclopentanone, dimethyl sulfoxide (DMSO), tetrahydrofuran, gamma-butyrolacton, N-dodecylpyrrolidone,
NVP, 1,3- dimethyl-2-imidazolinones.
3. the method that space-time synchronous ultrasound ball-milling method according to claim 1 peels off preparing graphite alkene, its feature exist
In：The reagent of peeling off is to configure the surfactant-aqueous systems formed, the surfactant bag by surfactant and water
Include：Sodium taurocholate, NaTDC, taurine sodium taurocholate, 3- [(3- courages amido propyl) dimethylamino] and acid inner salt, 12
Sodium alkyl benzene sulfonate, dodecyl sodium sulfate, didodecyldimethylammbromide bromide, n-dodecyl-β-D-maltoside, polyvinyl pyrrole
Alkanone, kayexalate, Myrj 45, PEO-PPOX-PEO three block are total to
Polymers, sorbitan monooleate APEO, Triton X-100, Cellulose nanocrystal.
4. the method for preparing graphite alkene is peeled off according to the space-time synchronous ultrasound ball-milling method described in claim 1, it is characterised in that：
The stripping reagent is conjugated structure molecular solvent, and the conjugated structure molecule includes：1- amino pyrene, 1- pyrenes methylamine hydrochloride,
Pyrene, benzylamine, 7,7,8,8- four cyano benzoquinones bismethane, 9- anthroic acids, 1- pyrenes butanol, 1- pyrenes carboxylic acid, 1- pyrenes butyric acid, 1- pyrenes
Azochlorosulfonate acid hydrate, 1- pyrenes sodium sulfonate, 6,8- dihydroxy -1,3- pyrenes sulfonate, 8- hydroxyl pyrene 1,3,6- trisulfonic acids sodium salt, 1,3,6,
8- pyrenes sodium salt, N, N- dimethyl diaza pyrenes villaumite, coronene tetramethyl acid potassium salt.
5. the method that space-time synchronous ultrasound ball-milling method according to claim 1 peels off preparing graphite alkene, its feature exist
In：The stripping reagent is ionic liquid, and the cation of the ionic liquid includes glyoxaline cation, pyridylium, quaternary ammonium
One or more in salt cation and quaternary phosphonium salt cation, the anion of the ionic liquid include tetrafluoroborate the moon from
One or more in son, hexafluorophosphoric acid salt anionic, chlorion and bromide ion.
6. the method that space-time synchronous ultrasound ball-milling method according to claim 1 peels off preparing graphite alkene, its feature exist
In：The reagent of peeling off is the ionic liquid-filler shear thickening system formed by ionic liquid-filler configuration；Wherein, it is described
The cation of ionic liquid includes one kind in glyoxaline cation, pyridylium, quaternary ammonium salt cationic and quaternary phosphonium salt cation
Or it is a variety of, the anion of the ionic liquid include tetrafluoro boric acid salt anionic, hexafluorophosphoric acid salt anionic, chlorion and bromine from
One or more in son；The filler includes silica, aluminum oxide, magnesia, zinc oxide, nickel oxide, cupric oxide, oxidation
One or more in beryllium, carbon ball, polymer microballoon and CNT, the size of the filler is 1nm~100 μm.
7. the side of preparing graphite alkene is peeled off according to space-time synchronous ultrasound ball-milling method according to any one of claims 1 to 5
Method, it is characterised in that：The graphite raw material includes native graphite, artificial synthesized graphite, expanded graphite, fluorographite and oxidation
One or more in graphite.
8. the side of preparing graphite alkene is peeled off according to space-time synchronous ultrasound ball-milling method according to any one of claims 1 to 5
Method, it is characterised in that：The ultrasonic power of the ultrasonic ball-grinding machine is 0.2~100kW, 100~750rpm of rotating speed.
9. the side of preparing graphite alkene is peeled off according to space-time synchronous ultrasound ball-milling method according to any one of claims 1 to 5
Method, it is characterised in that：Ball-milling Time is 2~96h under ultrasonic environment.
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| CN108584933A (en) * | 2018-07-15 | 2018-09-28 | 石梦成 | A kind of fluorinated graphene prepared by ionic liquid stripping |
| CN109216044A (en) * | 2018-09-12 | 2019-01-15 | 中南民族大学 | Graphene/metal oxide combination electrode material is prepared in situ in mechanochemical reaction |
| CN109231188A (en) * | 2018-11-26 | 2019-01-18 | 上海应用技术大学 | A method of nitrating fluorinated graphene is prepared using fluorographite |
| CN110042284A (en) * | 2019-05-08 | 2019-07-23 | 东南大学 | A kind of preparation method of high-strength aluminum alloy |
| CN110127684A (en) * | 2019-05-16 | 2019-08-16 | 南京工业大学 | The method that flow-type continuously removes graphite oxide and graphene oxide size classification |
| WO2022161091A1 (en) * | 2021-01-27 | 2022-08-04 | 广东邦普循环科技有限公司 | Method for preparing graphene by mechanical exfoliation and application thereof |
| GB2617023A (en) * | 2021-01-27 | 2023-09-27 | Guangdong Brunp Recycling Technology Co Ltd | Method for preparing graphene by mechanical exfoliation and application thereof |
| CN112939082A (en) * | 2021-01-28 | 2021-06-11 | 青岛科技大学 | Green, low-cost and efficient transition metal disulfide nanosheet preparation method |
| CN113800505A (en) * | 2021-08-02 | 2021-12-17 | 江苏杉元科技有限公司 | Graphene aqueous slurry and preparation method thereof |
| CN113675391A (en) * | 2021-08-05 | 2021-11-19 | 常熟理工学院 | Heterogeneous layered composite material for lithium ion battery cathode and preparation method thereof |
| CN113871615A (en) * | 2021-08-31 | 2021-12-31 | 兰州大学 | Fluorinated graphene electrode active material and preparation method and application thereof |
| CN113871615B (en) * | 2021-08-31 | 2024-03-15 | 兰州大学 | Fluorinated graphene electrode active material and preparation method and application thereof |
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