CN108502874A - A kind of method that electrochemistry assisting ultrasonic method prepares graphene dispersing solution - Google Patents
A kind of method that electrochemistry assisting ultrasonic method prepares graphene dispersing solution Download PDFInfo
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- CN108502874A CN108502874A CN201710118884.4A CN201710118884A CN108502874A CN 108502874 A CN108502874 A CN 108502874A CN 201710118884 A CN201710118884 A CN 201710118884A CN 108502874 A CN108502874 A CN 108502874A
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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
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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
- C01B2204/28—Solid content in solvents
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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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
A kind of method that electrochemistry assisting ultrasonic method prepares high-concentration stable graphene dispersing solution is disclosed, while cost-effective, the yield of graphene is improved, reduces the pollution to environment.The graphene dispersing solution concentration reaches as high as 11.47g/L, and 0.85 μm of graphene average-size, the number of plies is less, single layer rate 18%, few layer rate (1~3 layer) 76%.Preparation method includes：1, it configures certain density inorganic salts/inorganic acid aqueous solution and is used as electrolyte, electrolysis stripping graphite-rod anode under constant voltage, electrolysis spall filtering and washing is dried；2, above-mentioned solid material is added in solvent, is ultrasonically treated, supernatant liquid is collected by centrifugation and obtains graphene dispersing solution.This synthetic method is simple, easily controllable, environmentally protective, of low cost, it can be achieved that industrialized production.
Description
Technical field
The present invention relates to field of preparation of graphene more particularly to a kind of preparation methods of graphene dispersing solution.
Background technology
Graphene is a kind of novel two-dimentional carbon nanomaterial, conductivity and thermal conductivity, huge theory with superelevation
Specific surface area, high Young's modulus and tensile strength.These excellent specific properties of graphene make it in opto-electronic device, chemical-electrical
Source (such as solar cell, lithium ion battery), gas sensor, catalyst and pharmaceutical carrier, antistatic and heat sink material neck
There is huge potential application foreground in domain.Due to graphene large specific surface area, it is easy to happen aggregation between lamella, influences graphene
The performance of energy.The generation reunited in order to prevent, it is high usually by graphene dispersion in organic solvent or aqueous surfactant solution
Concentration graphene dispersing solution contributes to graphene to be more widely used in fields such as catalysis, composite materials.But it reports at present
The graphene dispersing solution concentration in road is generally relatively low, and the concentration for being dispersed in graphene in aqueous surfactant solution is usually no more than
1g/L, in organic solvent its concentration can reach 1.2g/L.Although graphene dispersing solution concentration can reach higher concentration,
Preparation process is complicated, and condition is harsh, and the time is long.So it is steady how with simple method to prepare high concentration in a relatively short period of time
Fixed graphene dispersing solution is a current problem.
Electrochemical process prepares graphene and has caused adequately to pay close attention in recent years, and this method is in preparation process without using height
The strong oxidizers such as potassium manganate can avoid destruction of the strong oxidizer to graphene-structured and performance；Without using alkali metal (K, Na)
Equal inflammable and explosive substances danger, does not introduce poisonous and harmful substance, environmental-friendly；Preparation condition is controllable；It is at low cost, it is suitable for big rule
Mould produces.But graphene sheet layer prepared by existing electrochemical method is thicker, and the yield of graphene is relatively low, and it cannot
Meets the needs of practical application well.
Invention content
The purpose of the present invention is exactly to solve the above-mentioned problems, to provide a kind of method preparing graphene dispersing solution, it has
Have the characteristics that simple and quick, environmentally protective, good dispersion, stability are good.
The basic imagination of the present invention is to prepare compound between graphite layers first with electrochemical method, makes the interlamellar spacing of graphite
Become larger, the molecular force between graphene weakens, and graphene sheet layer is easily peeled off in ultrasonic procedure.
The technical solution adopted by the present invention includes the following steps：
(1) certain density inorganic salts/inorganic acid aqueous solution is configured, as electrolyte；
(2) using the metal and alloy of chemistry and non-chemical stabilization or nonmetal conductor material as cathode, graphite rod is anode,
Constant voltage quick electrolysis removes graphite anode rod in the electrolytic solution, and control solution temperature is at 20~30 DEG C in electrolytic process；
(3) spall is collected by filtration, then washs, be dried to obtain graphite intercalation compound；
(4) above-mentioned graphite intercalation compound is added in organic solvent, is ultrasonically treated；
(5) supernatant liquid is collected by centrifugation and obtains graphene dispersing solution.
The electrolyte is selected from Na2SO4、(NH4)2HPO4、H2SO4、H3PO4One or more of, electrolyte in electrolyte
Total concentration is 0.1~1mol/L.
The cathode uses metal with chemistry and non-chemical stabilization and alloy or nonmetal conductor material, including platinum,
Gold, silver, copper and its alloy, titanium and its alloy, lead and its alloy, graphite.
The constant voltage is 8~14V.
The organic solvent is selected from methanol, isopropanol, tetrahydrofuran, toluene, dimethylbenzene, n,N-Dimethylformamide, N-
One or more of methyl pyrrolidone.
The initial concentration of the graphite intercalation compound in organic solvent is 20~50g/L.
The frequency of the ultrasonic cleaning machine is 42K~90K hertz.
The ultrasonic time is 1~9h.
Beneficial effects of the present invention：It is dark thick slurry, (1) dispersibility using graphene dispersing solution produced by the present invention
Good, for concentration up to 7~11.47g/L, the graphene product of lamella thin (1~10 layer) can be made in (2), and single layer rate is up to 18%；
(3) defect of obtained thin graphene product is few compared with redox graphene (rGO)；(4) at low cost, it is environmental-friendly.
Description of the drawings
The transmission electron microscope picture of 1 obtained thin graphene of Fig. 1 embodiment of the present invention；
The high power transmission electron microscope picture (a) of 1 obtained thin graphene of Fig. 2 embodiment of the present invention, partial enlarged view (b)；
The atomic force microscopy diagram of 1 obtained graphene of Fig. 3 embodiment of the present invention；
Graphene dispersing solution concentration prepared by Fig. 4 embodiment of the present invention 1 changes with time relational graph.
Specific implementation mode
Below in conjunction with specific implementation mode, the present invention is further illustrated, but the implementation model of the present invention is not limited with this
It encloses.
Graphene concentration determination in dispersion liquid：By the graphene dispersing solution of known concentration press gradient dilution, using it is ultraviolet can
See that spectrophotometer measures the absorbance of various concentration standard scores dispersion liquid respectively at 660nm wavelength.According to Lambert-Beer
Law (formula 1) draws standard curve, and fitting obtains absorption coefficient alpha660=3056Lg-1·m-1, show good
Lambert-Beer behaviors.
A/l=α C
The absorbance of graphene dispersing solution at A-660nm；L cuvette width (units：cm)；The places α -660nm graphene point
Absorptivity (the unit of dispersion liquid：L·g-1·m-1)；Concentration (the unit of C- graphene dispersing solutions：g/L)
Graphene size and its single layer rate test method：Graphene average-size is shone according to transmission electron microscope (TEM)
Piece statistics calculates；According to high resolution transmission electron microscope (HRTEM) edges and atomic force microscopy (AFM)
Graphene number of plies is counted, three layers and its hereinafter defined as few layer graphene, few layer of rate of graphene in product can be obtained accordingly
With single layer rate.
Case study on implementation 1
With the Na of 0.5mol/L2SO4For aqueous solution 100ml as electrolyte, diameter 6mm, the graphite rod conduct of length 6cm are positive
Pole, cathode are graphite rod as anode, and two electrodes are disposed vertically, parallel spacing 2cm.20 DEG C of electrolyte initial temperature, 14V
Graphite anode rod is removed in constant-potential electrolysis, until stripping terminates.It will be done in thermostatic drying chamber after electrolysis spall filtering washing
Dry dehydration.In conical flask, into dry sample, addition 30ml N-Methyl pyrrolidones are ultrasonically treated, and control sample
A concentration of 31g/L, supersonic frequency 40KHz, ultrasonic time 8h.Aforesaid liquid 2000rpm is centrifuged into 30min, collects upper layer
Obtain graphene dispersing solution.Calculate a concentration of 11.47g/L of graphene dispersing solution, 0.85 μm of graphene average-size, the number of plies compared with
It is few, single layer rate 18%, few layer rate 76%.The structure and morphology of graphene is shown in transmission electron microscope picture, sees Fig. 1.
Case study on implementation 2
With the Na of 0.3mol/L2SO4For aqueous solution 100ml as electrolyte, diameter 6mm, the graphite rod conduct of length 6cm are positive
Pole, anode are graphite rods, and cathode is platinum filament, and two electrodes are disposed vertically, parallel spacing 2cm.25 DEG C of electrolyte initial temperature,
Graphite anode rod is removed in 12V constant-potential electrolysis, until stripping terminates.Electrolysis spall is drained after washing in thermostatic drying chamber
Drying and dehydrating.30ml N, N- diformazans are added as the presoma for preparing graphene dispersing solution in solid after drying in conical flask
The initial concentration of base formamide, graphite intercalation compound is 31g/L, ultrasonic power 40KHz, ultrasonic time 8h.By above-mentioned liquid
Body 2000rpm centrifuges 30min, collects upper layer and obtains graphene dispersing solution.A concentration of 9.52g/L of graphene dispersing solution is calculated,
0.95 μm of graphene average-size, the number of plies is less, single layer rate 14%, few layer rate 64%.
Case study on implementation 3
With (the NH of 0.5mol/L4)2HPO4Aqueous solution 100ml as electrolyte, diameter 6mm, length 6cm graphite rod make
For anode, cathode is graphite rod as anode, and two electrodes are disposed vertically, parallel spacing 2cm.Electrolyte initial temperature 28
DEG C, graphite anode rod is removed in 14V constant-potential electrolysis, until stripping terminates.Electrolysis spall is drained after washing in freeze-day with constant temperature
Drying and dehydrating in case.15ml N, N- is added as the presoma for preparing graphene dispersing solution in solid after drying in conical flask
The initial concentration of dimethylformamide and 15ml tetrahydrofurans, graphite intercalation compound is 40g/L, supersonic frequency 50KHz, is surpassed
Sound time 9h.Aforesaid liquid 2000rpm is centrifuged into 30min, upper layer is collected and obtains graphene dispersing solution.Calculate graphene dispersion
A concentration of 11.01g/L of liquid, 0.82 μm of graphene average-size, the number of plies is less, single layer rate 14%, few layer rate 76%.
Case study on implementation 4
With the H of 0.5mol/L3PO4For aqueous solution 100ml as electrolyte, diameter 6mm, the graphite rod conduct of length 6cm are positive
Pole, cathode are graphite rod as anode, and two electrodes are disposed vertically, parallel spacing 2cm.23 DEG C of electrolyte initial temperature, 8V
Graphite anode rod is removed in constant-potential electrolysis, until stripping terminates.Electrolysis spall is drained and is done in thermostatic drying chamber after washing
Dry dehydration.30ml N- methylpyrroles are added as the presoma for preparing graphene dispersing solution in solid after drying in conical flask
The initial concentration of alkanone, graphite intercalation compound is 20g/L, supersonic frequency 70KHz, ultrasonic time 6h.By aforesaid liquid
2000rpm centrifuges 30min, collects upper layer and obtains graphene dispersing solution.Calculate a concentration of 7.51g/L of graphene dispersing solution, stone
0.98 μm of black alkene average-size, the number of plies is less, single layer rate 12%, few layer rate 72%.
Embodiment 5
Stability test：The graphene dispersing solution being prepared in embodiment 1 standing is made into natural subsidence experiment, every
48h takes upper layer dispersion liquid, analysis test graphene dispersion liquid concentration C.Sedimentation time t and graphene dispersing solution concentration are closed
Connection, exponential function are fitted (see Fig. 2), and the relationship of obtaining is：C=C0+C1e-t/τ, wherein C0It represents and stablizes graphene film in solvent
Concentration, C1The initial concentration of unstable graphene film is represented, τ represents sedimentation time constant.Fitting result is shown：C0=11.31g/
L；C1=0.16g/L；τ=258.74h.Time used in subsidence stage is longer, and the concentration of system has dropped 1.3%, this portion
Corresponding point sedimentation is graphene film unstable in system, it may be possible to large stretch of multi-layer graphene rather than unstripped stone
Ink.Remaining 98.7% graphene still kept stable by one month time, this part should be the graphite of single layer and few layer
Alkene.The result shows that the graphene dispersing solution of high concentration is highly stable, and graphene is few layer mostly.
Comparative example 1
Dry graphite sample is put into N-Methyl pyrrolidone, initial concentration 31g/L, carries out ultrasonic stripping,
Supersonic frequency is 40KHz, ultrasonic time 8h.Aforesaid liquid 2000rpm is centrifuged into 30min, upper layer is collected and obtains graphene dispersion
Liquid, a concentration of 1.2g/L of graphene dispersing solution, 1.15 μm of graphene average-size, the number of plies is more, single layer rate 4%, few layer rate
20%.
Claims (7)
1. a kind of method that electrochemistry assisting ultrasonic method prepares graphene dispersing solution, which is characterized in that include the following steps：
(1) certain density inorganic salts/inorganic acid aqueous solution is configured, as electrolyte；
(2) using the metal and alloy of chemistry and non-chemical stabilization or nonmetal conductor material as cathode, graphite rod is anode, in electricity
It solves constant voltage quick electrolysis in liquid and removes graphite anode rod, control solution temperature is at 20~30 DEG C in electrolytic process；
(3) spall is collected by filtration, then washs, be dried to obtain graphite intercalation compound；
(4) above-mentioned graphite intercalation compound is added in organic solvent, ultrasonication；
(5) supernatant liquid is collected by centrifugation and obtains graphene dispersing solution.
2. according to the method described in claim 1, it is characterized in that, the inorganic salts/inorganic acid electrolyte is selected from Na2SO4、
(NH4)2HPO4、H2SO4、H3PO4One or more of；The electrolyte total concentration of solutes is 0.1~1mol/L.
3. according to the method described in claim 1, it is characterized in that, the cathode be selected from platinum, gold, silver, copper and its alloy, titanium and
Its alloy, lead and its alloy, graphite.
4. such as claims 1 to 3 any one of them method, feature exists, and constant voltage is 8~14V.
5. according to the method described in claim 4, it is characterized in that, organic solvent be methanol, isopropanol, tetrahydrofuran, toluene,
One or more of dimethylbenzene, n,N-Dimethylformamide, N-Methyl pyrrolidone.
6. according to method as claimed in claim 5, which is characterized in that the frequency of ultrasonic cleaner is 40K~90K hertz,
1~9h of processing time.
7. graphene dispersing solution prepared by method according to claims 1 to 6.
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Cited By (9)
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|---|---|---|---|---|
| CN110357087A (en) * | 2019-08-14 | 2019-10-22 | 中国科学院兰州化学物理研究所 | A method of graphene oxide is prepared based on high concentration inorganic salt solution removing |
| CN110433771A (en) * | 2019-07-22 | 2019-11-12 | 杭州电子科技大学 | A kind of pair of Co (II) has the functionalized carbon nano material and preparation method thereof of absorption property |
| CN110449574A (en) * | 2019-08-05 | 2019-11-15 | 上海世系新材料有限公司 | A kind of preparation method of low defect graphene coated aluminium powder particle |
| CN110697690A (en) * | 2019-08-15 | 2020-01-17 | 赵宁 | Preparation method for preparing graphene by electrolytic method |
| CN110724985A (en) * | 2019-11-13 | 2020-01-24 | 珠海市玛斯特五金塑胶制品有限公司 | Sealing treatment liquid, transparent corrosion-resistant film and preparation method thereof |
| CN111924832A (en) * | 2020-09-23 | 2020-11-13 | 广西师范大学 | Device and method for producing graphene by electrochemically stripping graphite from electrode array |
| CN112239203A (en) * | 2019-07-16 | 2021-01-19 | 中国科学院上海微***与信息技术研究所 | Electrochemical preparation method of porous graphene dispersion liquid |
| CN113753870A (en) * | 2021-09-30 | 2021-12-07 | 海南大学 | GeP nanosheet negative electrode for lithium ion battery and ultrasonic-assisted rapid stripping preparation method thereof |
| CN114555520A (en) * | 2019-11-15 | 2022-05-27 | 株式会社Lg新能源 | Preparation method of graphene nanosheet |
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Cited By (13)
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| CN112239203A (en) * | 2019-07-16 | 2021-01-19 | 中国科学院上海微***与信息技术研究所 | Electrochemical preparation method of porous graphene dispersion liquid |
| CN112239203B (en) * | 2019-07-16 | 2022-09-09 | 中国科学院上海微***与信息技术研究所 | Electrochemical preparation method of porous graphene dispersion liquid |
| CN110433771A (en) * | 2019-07-22 | 2019-11-12 | 杭州电子科技大学 | A kind of pair of Co (II) has the functionalized carbon nano material and preparation method thereof of absorption property |
| CN110449574A (en) * | 2019-08-05 | 2019-11-15 | 上海世系新材料有限公司 | A kind of preparation method of low defect graphene coated aluminium powder particle |
| CN110449574B (en) * | 2019-08-05 | 2021-11-09 | 上海世系新材料有限公司 | Preparation method of low-defect graphene-coated aluminum powder particles |
| CN110357087A (en) * | 2019-08-14 | 2019-10-22 | 中国科学院兰州化学物理研究所 | A method of graphene oxide is prepared based on high concentration inorganic salt solution removing |
| CN110697690A (en) * | 2019-08-15 | 2020-01-17 | 赵宁 | Preparation method for preparing graphene by electrolytic method |
| CN110724985B (en) * | 2019-11-13 | 2021-03-26 | 珠海市玛斯特五金塑胶制品有限公司 | Sealing treatment liquid, transparent corrosion-resistant film and preparation method thereof |
| CN110724985A (en) * | 2019-11-13 | 2020-01-24 | 珠海市玛斯特五金塑胶制品有限公司 | Sealing treatment liquid, transparent corrosion-resistant film and preparation method thereof |
| CN114555520A (en) * | 2019-11-15 | 2022-05-27 | 株式会社Lg新能源 | Preparation method of graphene nanosheet |
| CN114555520B (en) * | 2019-11-15 | 2024-01-02 | 株式会社Lg新能源 | Preparation method of graphene nanosheets |
| CN111924832A (en) * | 2020-09-23 | 2020-11-13 | 广西师范大学 | Device and method for producing graphene by electrochemically stripping graphite from electrode array |
| CN113753870A (en) * | 2021-09-30 | 2021-12-07 | 海南大学 | GeP nanosheet negative electrode for lithium ion battery and ultrasonic-assisted rapid stripping preparation method thereof |
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