CN102701187B - Graphene prepared by a kind of preparation method of Graphene and use the method - Google Patents
Graphene prepared by a kind of preparation method of Graphene and use the method Download PDFInfo
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Abstract
The preparation method that the present invention relates to a kind of Graphene and the Graphene using the method to prepare, it is characterized in that, the present invention take graphite as raw material, obtaining compound between graphite layers, then peeling off described compound between graphite layers and obtaining Graphene by inserting metal in graphite layers.Length and the width of the Graphene using the method to prepare are 5 ~ 15000nm, and thickness is 0.3 ~ 15nm.Advantage of the present invention is: raw material sources are extensive, with low cost, preparation method is easy, product performance are stablized controlled, is applicable to suitability for industrialized production.
Description
[technical field]
The present invention relates to technical field of graphene, specifically, the preparation method that the present invention relates to a kind of Graphene and the Graphene using the method to prepare.
[background technology]
Graphene (Graphene) is the allotropic substance of a kind of carbon be recently familiar with for the mankind after soccerballene, carbon nanotube.Graphene is that a kind of carbon atom is with sp
2hybridized orbital Cheng Jian, the carbon material of the individual layer bi-dimensional cellular shape crystalline network formed with six-membered ring structure.The structure of this uniqueness of Graphene brings series of novel, special character to it, such as water white transparency (absorb light intensity is only 2.3%), electric conductivity high (single-layer graphene electric conductivity is close with copper), (tensile strength can reach 50 ~ 200GPa to excellent in mechanical performance, Young's modulus can reach 1TPa, and the tensile strength of single-layer graphene is 100 times of condition of equivalent thickness steel disc).Above characteristic makes Graphene have broad application prospects in many new forms of energy, field of new such as touch-screen, solar cell, aerospace materials.Therefore the preparation of Graphene and character research thereof have become the focus in nano science research in recent years.
The preparation method of Graphene is summed up, and mainly contains micromechanics stripping method, chemical Vapor deposition process (CVD), reduction-oxidation graphite method etc.
Wherein, micromechanics stripping method successfully prepares the method for Graphene the earliest.The method utilizes the tear-off repeatedly of adhesive tape that graphene film is separated (K.S.Novoselov from highly oriented pyrolytic graphite, etal.Science, 306,666 (2004)), although adopt the method can prepare the Graphene of high-quality, but the method expensive starting materials, preparation process is seriously consuming time, cannot realize scale operation.
Chemical Vapor deposition process is under pyrocarbon hydrogen compound (as methane) atmosphere, make the carbon laydown in hydrocarbon polymer to transition metal substrate thus obtained Graphene (JessicaCampos-Delgado, etal.NanoLetters, 8,9 (2008)).The method can obtain larger-size grapheme material, but manufacturing cost is too high and the graphene product number of plies of gained is difficult to control, and then limits the application of product.
Reduction-oxidation graphite method prepares the main method of Graphene at present in a large number.The method, first by graphite oxidation, then obtains graphene oxide by stripping, finally the graphene oxide obtained is obtained Graphene by reduction.Although this method can prepare Graphene (VincentC., etal.NatNanotech, 4 in a large number, 25 (2008)), but, because this method relates to oxidation, reduction process, final gained Graphene still can contain partial oxidation group, and these oxide groups destroy the sp of Graphene
2structure, can cause the performance of Graphene, particularly conductivity and have a strong impact on.
For solving above-mentioned preparation method's Problems existing, the Patents PART of current domestic existence is as follows.
Chinese Patent Application No.: 200910084879.1, patent name: the preparation method of Graphene.This inventive method is reacted in ionic liquid by carbon nanotube and oxygenant and obtained Graphene.The method step is simple, easy handling, is applicable to large-scale commercial production.
Chinese Patent Application No.: 200880112966.7, patent name: a kind of preparation method of two-dimension single layer plumbago alkene.The catalyzer of single-layer graphene is first prepared in this invention, passes into carbon source Pintsch process in an inert atmosphere afterwards and obtain two-dimension single layer plumbago alkene in the container that catalyzer is housed.
In sum, the technology preparing Graphene at present can't meet that preparation method is simple, with low cost, product performance stablize the industrialization basic demands such as controlled, and this just significantly limit Graphene in application that is wider, more wide field.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, the Graphene a kind of preparation method of Graphene being provided and using the method to prepare.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for Graphene take graphite as raw material, obtaining compound between graphite layers, then peeling off described compound between graphite layers and obtaining Graphene by inserting metal in graphite layers.
The selection of described graphite there is no particular restriction, can comprise natural graphite, synthetic graphite, specifically, comprises natural flake graphite, highly oriented pyrolytic graphite or special spherical graphite etc.Therefore raw material sources object extensive, with low cost can be reached.
Described insertion metal be one in basic metal, alkaline-earth metal, rare earth metal, two or more:
Described basic metal is lithium (Li), sodium (Na), potassium (K), rubidium (Ru), caesium (Cs), francium (Fr);
Described alkaline-earth metal is beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra);
Described rare earth metal is lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), yttrium (Y);
Also can be to be selected from aforementioned metal two or more, as: lithium (Li)/calcium (Ca), potassium (K)/magnesium (Mg), potassium (K)/scandium (Sc), magnesium (Mg)/calcium (Ca), lithium (Li)/magnesium (Mg)/lanthanum (La) etc.
Insert metal with in basic metal, alkaline-earth metal a kind of, two or more is preferred, comparatively preferably basic metal, more preferably lithium (Li), potassium (K), rubidium (Ru), caesium (Cs), most preferably lithium (Li).
The preparation method of described compound between graphite layers is selected from a kind of, two or more combination in following method: solid phase pressurization, scorification, two warm area vapor transportation methods, liquid phase interpolation, molten salt electrolysis of metals method, battery charging and discharging method.
Wherein, described solid phase pressurization: after being mixed with graphite matrix by metal-powder, reaction generates compound between graphite layers under an increased pressure, use this method key to be to only have when the vapour pressure of metal exceedes a certain threshold value, insertion reaction just can carry out.But the too high side reaction easily causing metal and graphite Formed compound of temperature, so temperature of reaction must control within the specific limits, for needing very high-temperature that the metal of insertion reaction could occur, needs pressurization to reduce temperature of reaction.
Described scorification is directly mixed with metal-powder by graphite, obtain compound between graphite layers by single heat source reacting by heating, this method speed of response is fast, reactive system and process simple, be suitable for a large amount of synthesis, but after reaction, the reactant be attached on compound between graphite layers is difficult to remove.
Two described warm area vapor transportation methods will be for being inserted into material and graphite is respectively charged into heat-resistant glass tube both sides, and the steam that inset heating evaporation is produced and graphite react.The temperature inserting material side in experiment is higher than the temperature of graphite side, is beneficial to insert material and forms steam, prevent the compound between graphite layers generated from when temperature is too high, decomposition reaction occurring simultaneously.The advantage of this method is easy to separated product and reactant after reaction terminates, and shortcoming is that reaction unit is complicated, is difficult to synthesize in a large number, and long reaction time, temperature is high, need operate under vacuum.
The insertion metal be in a liquid state mixes with graphite by described liquid phase interpolation, carries out reacting and generating compound between graphite layers, and in reaction, temperature, the stage structure of time to product have a significant impact.This method equipment is simple, and speed of response is fast, is suitable for a large amount of synthesis, but because require must by metal melting, in actually operating, temperature is large to melting point metal dependency.
Described molten salt electrolysis of metals method, to insert metal melting salt for ionogen, is that electrode forms chemical system with graphite, is inserted into graphite as anode, prepares compound between graphite layers by the control of adjustment current potential, electricity.This method synthesis device is simple, and resultant quantity is large, and weak point is that the stability of synthetic product is poorer than additive method.
Namely described battery charging and discharging method is specifically divided into two kinds from name is known, and one is battery discharge method, and another kind is battery mise-a-la-masse method.Wherein said battery discharge method take graphite as positive pole, and metal is negative pole, adds electrolytic solution and form battery system.Run according to default discharge step, metal is inserted in graphite and forms compound between graphite layers;
Wherein said battery mise-a-la-masse method or does not seldom change with agent structure in process of charging, and the metal do not reacted with electrolytic solution is intercalation compound for positive pole, and graphite is negative pole, adds electrolytic solution and form battery system.Run according to preset charged step, metal is inserted in graphite and forms compound between graphite layers.
This method technique is simple, and reaction conditions is gentle, and by default discharge and recharge end condition, obtains the compound between graphite layers that exponent number is controlled, be suitable for suitability for industrialized production.
In a preferred embodiment, the method preparing compound between graphite layers is preferred with solid phase pressurization, scorification, liquid phase interpolation, molten salt electrolysis of metals method and battery charging and discharging method, more preferably electrolytic process and battery charging and discharging method, most preferably battery charging and discharging method.
The method of described stripping compound between graphite layers is selected from a kind of, two or more combination in following method: mechanically peel, stripper are peeled off, electrolytic stripping.
Described mechanically peel makes its bending, depression, the power of swiping, be pressed into or fracture, thus the method separating Graphene for using compound between graphite layers.The example of mechanically peel can be utilize adhesive tape tear-off compound between graphite layers repeatedly, makes it thinning, thus obtains Graphene.Also can be utilize the tipless cantilever of atomic force microscope (AFM) to swipe the compound between graphite layers be fixed wtih, obtain the thin slice scraped and continue abovementioned steps, finally obtain Graphene.Also can be utilize ball mill to carry out ball milling to the compound between graphite layers powder be scattered in organic solvent, thus obtain Graphene.Use mechanically peel can not on gained Graphene introducing hetero-atoms, but gained Graphene out-of-shape, and preparation process is consuming time longer.
It is ionogen that described electrolytic stripping inserts metal melting salt, be that electrode forms chemical system with graphite, compound between graphite layers is as anode, and metal electrolysis being generated by the control of adjustment current potential, electricity continues to insert compound between graphite layers interlayer thus peels off obtained Graphene.Use electrolytic stripping can prepare Graphene on a large scale, but gained Graphene can leave impurity, such as metal-salt.And whole reaction process needs higher temperature, reaction environment is required comparatively harsh.
Described stripper is peeled off and two kinds of strippers can be utilized to peel off: one is utilize the stripper that can react with compound between graphite layers, the gas discharged by reaction or bulking effect expand graphite layers distance further, make graphite flake layer mutually away to the constraint breaking away from Van der Waals force to each other, finally peel off and obtain Graphene; Two is the strippers adopting surface energy close with graphite, because the entropy of mixing of stripper and graphite can be reduced when surface energy is close, be similar to " similar mix " principle, stripper so just can be allowed to be inserted in compound between graphite layers, continue to increase graphite layers distance, thus stripping compound between graphite layers obtains Graphene.The surface tension of selected stripper need at 10-70mJ/m
2, more preferably at 20-50mJ/m
2scope in; Above-mentioned surface tension numerical value is all sessile drop method test gained at 20 DEG C.Use stripper strip operation simple, stripper wide material sources, are mostly the chemical reagent often had, can not on obtained Graphene introducing hetero-atoms.
Stripping means most preferably stripper is peeled off.
Described stripper be selected from one in inorganic liquid and organic liquid, two or more.
Described inorganic liquid is selected from water, inorganic acid aqueous solution, water phase surfactant mixture.
Described inorganic aqueous acid example is the aqueous solution, dilute sulphuric acid, dust technology etc. of hydrogenchloride
Described tensio-active agent example is polyoxyethylene stearic acid ester (Brij76), cetyl trimethylammonium bromide (CTAB), Tetradecyl Trimethyl Ammonium Bromide (TTAB), 1-pyridine acid (PBA), sodium lauryl sulphate (SDS), Sodium dodecylbenzene sulfonate (SDBS), lithium dodecyl sulfate (LDS), Sodium cholic acid (SC), Sodium desoxycholate (DOC), cow-bezoar Sodium desoxycholate (TDOC), sodium (CHAPS) in 3-[3-(courage amido propyl) dimethylamino] propanesulfonic acid, sodium polystyrene sulfonate (PSS), polyvinylpyrrolidone (PVP), dodecyl-β-D-Maltose glycosides (DBDM), nonoxynolum (IGEPALCO-890), octadecanoic acid ester of polyethylene glycol (Tween80) etc.
Described organic liquid is selected from alcohol, ketone, ester, amine, sulfone, chlorobenzene, organic acid, ionic liquid.
Wherein said alcohol is the alcohol containing 1-6 carbon atom.Example can be methyl alcohol, ethanol, ethylene glycol, 1-propyl alcohol, 2-propyl alcohol, 1,2-PD, 1,3-PD, glycerol, n-butyl alcohol, 1-amylalcohol, 1-hexanol etc.;
Wherein said acid is the acid that fowl has 1-6 carbon atom.Example can be formic acid, acetic acid, oxalic acid, 1-propionic acid, 2-propionic acid, 1,2-propanedioic acid, 1,3-propanedioic acid, the third three acid, 1-butyric acid, 1-valeric acid, 1-caproic acid etc.;
The example of wherein said ketone can be acetone, 1-Methyl-2-Pyrrolidone, NVP, octylpyrrolidone, dodecyl pyrrolidone, DMI etc.;
The example of wherein said ester can be gamma-butyrolactone, peruscabin etc.;
The example of wherein said amine can be dimethyl formamide, DMA, DMF etc.;
The example of wherein said sulfone can be dimethyl sulfoxide (DMSO) etc.;
The example of wherein said chlorobenzene can be orthodichlorobenzene etc.;
The example of wherein said ionic liquid can be [Bmim] [BF
4], [Bmim] [Tf
2n], [C
4mim] [PF
6], [C
8mim] [PF
6], [C
4mim] Cl, [C
8mim] Cl etc.
Also the mixture of two or more composition of aforesaid liquid can be selected from, as: water/methyl alcohol, water/ethanol, water/formic acid, ethanol/acetic acid, water/ethanol/acetic acid, N-Methyl pyrrolidone/water, [BMIm] [BF
4]/water, [C
4mim] [PF
6]/dimethyl formamide etc.
Length and the width of the Graphene obtained according to method of the present invention are 5 ~ 15000nm, and thickness is 0.3 ~ 15nm.The thickness of known single-layer graphene is about 0.335nm, and therefore the thickness of Graphene is not less than 0.3nm.Thickness due to Graphene of the present invention is recorded by atomic force microscope (AFM), but the interaction between AFM probe and substrate and Graphene can bring measuring error, therefore Graphene thickness generally about the 0.4 ~ 0.5nm larger than actual value that record of AFM, concrete example, the single-layer graphene thickness that AFM records is about 0.8nm, the thickness of bilayer graphene is about 1.1nm, and three layer graphene thickness are about 1.5nm.Based on this reason, in aftermentioned embodiment, the thickness of listed Graphene is owing to being all adopt AFM to record, and therefore numerical value is all greater than 0.8.In the present invention, gained Graphene thickness is at 0.3 ~ 15nm, and the number of plies is between about 1 ~ 45 layer.
The productive rate of Graphene is quality and the raw graphite mass ratio of obtained Graphene.The quality of Graphene directly can weigh final solid graphene and obtain, and also can derive from the concentration of Graphene in graphene dispersing solution.In graphene dispersing solution, the concentration of Graphene utilizes the absorbancy (testing tool as: 722N visible spectrophotometer (Shanghai Precision Scientific Apparatus Co., Ltd's manufacture)) measuring graphene dispersing solution, follows that Law of Lambert-Beer carries out calculating.
The structural information of compound between graphite layers can utilize X ray diffracting spectrum (XRD) to measure (testing tool as: D/MAX2550VB/PC (Japanese Rigaku company manufactures), target source: copper target).
The thickness number of plies of described Graphene and length and width size can utilize atomic force microscope images (AFM) to carry out determining (testing tool as: NanoScopeIIIaMultiModeAFM (manufacture of Veeco company of the U.S.), operator scheme: tapping-mode).
The length and width size of described Graphene also can carry out determining with scanning electronic microscope (SEM) (testing tool as: SEM (JSM-6360LV) (Japanese JEOL company manufactures)).
The defect level of Graphene can utilize the strength ratio (I at D peak and G peak in Raman spectrum (Raman) figure
d/ I
g) value determines, I
d/ I
gbe worth larger, the defect contained by Graphene more (testing tool as: inVia+Reflex (manufacture of Renishaw company of Britain), laser wavelength: 514nm).
Compared with prior art, positively effect of the present invention is:
(1) raw material sources are extensive, with low cost, various types of graphite all can be used for preparing Graphene, stripper used mostly also is conventional chemical reagent, conveniently be easy to get, metal used mostly is common metal, particularly lithium, and its reactive behavior is moderate, can ensure that the success of stripping process is carried out, also easily as the too active metal such as sodium, potassium can not cause fire;
(2) easy, the product performance of preparation method are stablized controlled, are applicable to suitability for industrialized production;
(3) for needing Graphene to contain more defect when support of the catalyst and electrode materials, Graphene itself prepared by the inventive method has more defect, without the need to further process, namely can be used as support of the catalyst or electrode materials.
[accompanying drawing explanation]
Fig. 1 is the method process flow diagram that the present invention prepares Graphene.
Fig. 2 obtains the lithium-compound between graphite layers of single order and X-ray diffraction (XRD) figure of raw graphite according to embodiment 1, and wherein a refers to compound between graphite layers, and b refers to graphite.
Fig. 3 be according to embodiment 1 prepare Graphene at Si0
2atomic force microscope (AFM) Fig. 5 .00 × 5.00 μm size (a) on/Si substrate, 1.95 × 1.95 μm of sizes (b) and altitude profile figure (c).
Fig. 4 is the Raman spectrogram of the Graphene according to embodiment 1 preparation.
Fig. 5 is scanning electronic microscope (SEM) figure of the Graphene according to embodiment 3 preparation.
[embodiment]
The embodiment of the preparation method of a kind of Graphene of the present invention is below provided.
Embodiment 1
Battery discharge legal system is for compound between graphite layers
By special spherical graphite SSG (active material) (deriving from Loudi, Hunan Hui Yu Science and Technology Ltd.), acetylene black (conductive agent, particle diameter: about 10nm), polyvinylidene difluoride (PVDF) PVDF (binding agent) in mass ratio 8: 1: 1 ratio mixing, adding 1-Methyl-2-Pyrrolidone (NMP) makes PVDF concentration within the scope of 0.005 ~ 0.03g/ml, stir, furnishing pasty slurry.Its uniform spreading is overlayed on Copper Foil, study carefully entirely until solvent evaporates, punch tool is utilized to obtain circular graphitic electrode slice, by the vacuum-drying after 12 hours at 80 DEG C of obtained Graphite Electrodes sheet, select metal lithium sheet as battery cathode, Graphite Electrodes is as anode, lithium hexafluoro phosphate being dissolved in volume ratio is that solution in EC/EMC/DMC (NSC 11801/Methyl ethyl carbonate/methylcarbonate) ternary mixed solvent of 1: 1: 1 is as electrolytic solution, barrier film adopts polypropylene porous film, is less than assembled battery in the glove box of 1ppm in water, oxygen level.
Then (testing tool is as: BTS high accuracy battery detection system (new Weir Electronics Co., Ltd. of China manufactures) battery of assembling to be carried out impulsive discharge, model: CT-3008W-5V10mA-S1), after arranging according to parameter given below, impulsive discharge can be carried out: in each circulation, carry out constant-current discharge 5 minutes with the discharge rate of 0.05C, leave standstill 12 minutes, circulate successively.Pulse discharge time is 7 days, then stops electric discharge, disassembles battery, take out the single order lithium-compound between graphite layers of negative pole in the glove box that water, oxygen level are less than 1ppm.After liquid volatilization to be electrolysed, lithium-compound between graphite layers is scraped gently from copper sheet from, place in agate mortar and grind to form uniform powder, pour into rapidly deionized water take out the lithium-compound between graphite layers of powdery in glove box after, deionized water described herein, as stripper, is peeled off the metallic lithium in lithium-compound between graphite layers and obtained Graphene.
Utilize spectrophotometer to record the concentration of gained Graphene aqueous dispersions, thus obtain the output of the Graphene obtained, and then obtain productive rate.The Graphene productive rate adopting preceding method gained the present embodiment is 0.56%.
Fig. 2 is the single order compound between graphite layers of embodiment 1 gained lithium and the XRD figure of raw graphite.Can find out: after graphite layers inserts metallic lithium, originally disappear at the graphite features peak at 26.6 ° of places, replacing is near 24 °, occurred an obvious spike.This phenomenon demonstrates the formation of single order lithium-compound between graphite layers.
Fig. 3 is the AFM figure that embodiment 1 obtains Graphene, and the Graphene height that figure (c) is corresponding is 0.8nm, is individual layer.Graphene thickness is between 0.8 ~ 7nm, and the number of plies is between about 1 ~ 20 layer.Length and width are all between 100nm ~ 5000nm.
Fig. 4 gives the Raman spectrogram (X-coordinate is wave number, and ordinate zou is intensity) of Graphene prepared by embodiment 1, can find out, G peak illustrates the existence of graphite-structure in Graphene, and D peak illustrates the existence of defect in Graphene.The strength ratio I at D peak and G peak
d/ I
gvalue is 0.69.
Embodiment 2
Battery discharge legal system is for compound between graphite layers
Except pulse discharge time is 3 beyond the highest heavens, all the other operations are identical with embodiment 1, thus obtain second order lithium-compound between graphite layers.Final gained Graphene productive rate is 0.59%, and gained Graphene thickness is between 2.1 ~ 9.2, and namely the number of plies is between about 5 ~ 26 layers, length and width all between 100 ~ 6300nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.68.
Embodiment 3
Battery discharge legal system is for compound between graphite layers
Except pulse discharge time is 2 beyond the highest heavens, all the other operations are identical with embodiment 1, thus obtain three rank lithium-compound between graphite layers.Final gained Graphene productive rate is 0.45%, and gained Graphene thickness is between 4.5 ~ 11.3, and namely the number of plies is between about 12 ~ 32 layers, length and width all between 130 ~ 7000nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.67.
Embodiment 4
Battery discharge legal system is for compound between graphite layers
Except pulse discharge time is 32 hours, all the other operations are identical with embodiment 1, thus obtain quadravalence lithium-compound between graphite layers.Final gained Graphene productive rate is 0.32%, and gained Graphene thickness is between 6.5 ~ 14.4, and namely the number of plies is between about 18 ~ 42 layers, length and width all between 130 ~ 6800nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.66.
Embodiment 5
Battery discharge legal system is for compound between graphite layers
Be connected by the battery positive and negative polarities of the assembling described in embodiment 1, carry out short circuit dischange 48 hours, all the other operations are identical with embodiment 1.Final gained Graphene productive rate is 0.62%, and gained Graphene thickness is between 1.5 ~ 8.2, and namely the number of plies is between about 3 ~ 24 layers, length and width all between 50 ~ 6500nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.71.
Embodiment 6
Battery mise-a-la-masse method prepares compound between graphite layers.
By cobalt acid lithium (active material (Beijing Zhongxinguoan Mengguli Electric Source Technology Co., Ltd)), acetylene black (conductive agent, particle diameter: about 10nm), polyvinylidene difluoride (PVDF) PVDF (binding agent) in mass ratio 90: 5: 5 ratio mixing, adding 1-Methyl-2-Pyrrolidone (NMP) makes polyvinylidene difluoride (PVDF) PVDF concentration within the scope of 0.005 ~ 0.03g/ml, stir, furnishing pasty slurry.Its uniform spreading is overlayed on aluminium foil, after solvent evaporates is complete, punch tool is utilized to obtain anode electrode sheet, by the vacuum-drying after 12 hours at 120 DEG C of obtained anode electrode sheet, select natural graphite (particle diameter 20 ~ 30 μm) as battery cathode, lithium hexafluoro phosphate being dissolved in volume ratio is that solution in EC/EMC/DMC (NSC 11801/Methyl ethyl carbonate/methylcarbonate) ternary mixed solvent of 1: 1: 1 is as electrolytic solution, barrier film adopts polypropylene porous film, is less than assembled battery in the glove box of 1ppm in water, oxygen level.
Then the battery of assembling is carried out constant current charge with the charge rate of 0.2C and rise to 4.2V to cell voltage.Carry out constant voltage charge afterwards and be down to 0.02C to charge rate, after shelving 30min, again with the charge rate of 0.2C, constant current charge is carried out to battery and be first charged to 4.35V, constant voltage charge to charge rate is down to 0.02C (testing tool as: BTS high accuracy battery detection system (new Weir Electronics Co., Ltd. of China manufactures), model: CT-3008W-5V10mA-S1) again.Then stop charging, in the glove box that water, oxygen level are less than 1ppm, disassemble battery, take out the single order lithium-compound between graphite layers of negative pole.After liquid volatilization to be electrolysed, lithium-compound between graphite layers is scraped gently from copper sheet from, place in agate mortar and grind to form uniform powder, pour into rapidly deionized water take out the lithium-compound between graphite layers of powdery in glove box after, deionized water described herein, as stripper, is peeled off the metallic lithium in lithium-compound between graphite layers and obtained Graphene.Final gained Graphene productive rate is 0.61%, and gained Graphene thickness is between 0.8 ~ 12nm, and namely the number of plies is between about 1 ~ 35 layer, length and width all between 100 ~ 15000nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.74.
Figure 5 shows that the SEM figure of wherein a slice Graphene that embodiment 6 is obtained.As can be seen from this SEM figure, it is folding curling that this Graphene there occurs to a certain degree.Be about as 10600nm after this Graphene studies carefully full expand, be widely about 10000nm.
Embodiment 7
A, solid phase pressurization prepare compound between graphite layers.
Be less than in the glove box of 1ppm in water, oxygen level, graphite (particle diameter 40 ~ 50 μm) 1.44g and lithium (particle diameter 200 ~ 400 μm) 2g is mixed, is placed in tightness system and is forced into 15kbar.Be heated to 200 DEG C afterwards, keep this pressure and temperature 24 hours, lithium-compound between graphite layers can be obtained.
B, prepare Graphene by the compound between graphite layers obtained.
The retained material of removing lithium-compound between graphite layers surface attachment, places in agate mortar and grinds to form uniform powder, pour into rapidly deionized water, react immediately, thus obtain Graphene in glove box after taking out the lithium-compound between graphite layers of powdery.Final gained Graphene productive rate is 0.61%, and gained Graphene thickness is between 1.8 ~ 9.0nm, and namely the number of plies is between about 4 ~ 26 layers, length and width all between 90 ~ 8000nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.75.
Embodiment 8
A, solid phase pressurization prepare compound between graphite layers.
Be less than in the glove box of 1ppm in water, oxygen level, graphite (particle diameter 40 ~ 50 μm) 1.44g and ytterbium (particle diameter 300 ~ 500 μm) 4g is mixed, is placed in tightness system and is forced into 20kbar.Be heated to 390 DEG C afterwards, keep this pressure and temperature two weeks, ytterbium-compound between graphite layers can be obtained.
B, prepare Graphene by the compound between graphite layers obtained.
The retained material of removing ytterbium-compound between graphite layers surface attachment, place in agate mortar and grind to form uniform powder, pour into rapidly deionized water take out the ytterbium-compound between graphite layers of powdery in glove box after, ytterbium-compound between graphite layers and deionized water react, deionized water is as stripper herein, metallic lithium in ytterbium-compound between graphite layers is peeled off, thus obtains Graphene.Final gained Graphene productive rate is 0.42%, and gained Graphene thickness is between 5.6 ~ 14nm, and namely the number of plies is between about 15 ~ 40 layers, length and width all between 200 ~ 7600nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.79.
Embodiment 9
A, solid phase pressurization prepare compound between graphite layers.
Be less than in the glove box of 1ppm in water, oxygen level, graphite (diameter 40 ~ 50 μm) 1.44g and thulium (particle diameter 300 ~ 500 μm) 4g is mixed, is placed in tightness system and is forced into 20kbar.Be heated to 500 DEG C afterwards, keep this pressure and temperature two weeks, thulium-compound between graphite layers can be obtained.
B, prepare Graphene by the compound between graphite layers obtained.
The retained material of removing thulium-compound between graphite layers surface attachment, places in agate mortar and grinds to form homogeneous powder, pour into rapidly deionized water, react immediately, thus obtain Graphene in glove box after taking out the thulium-compound between graphite layers of powdery.Final gained Graphene productive rate is 0.40%, and gained Graphene thickness is between 4.7 ~ 14.8nm, and namely the number of plies is between about 13 ~ 43 layers, length and width all between 340 ~ 7000nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.78.
Embodiment 10
A, scorification prepare compound between graphite layers.
Be less than in the glove box of 1ppm in water, oxygen level, the natural graphite of constant temperature 400 DEG C after degassed 12 hours (graphitiferous carbon 97 ~ 98%, particle diameter 90 ~ 145 μm) 9.6g is under vacuo placed in flat 100ml there-necked flask with the potassium 3.9g being cut into irregular bulk together with a stirrer.There-necked flask is sealed, takes out glove box, connect vacuum line, vacuumize, and pass into helium, make bottle internal gas pressure a little more than normal atmosphere.Start heating afterwards, temperature melts completely to potassium when about 100 DEG C, now starts to carry out fiercer stirring.After temperature rises to 170 DEG C, be incubated 45 minutes, cooling afterwards obtains the potassium-compound between graphite layers of single order.
B, prepare Graphene by the compound between graphite layers obtained.
The retained material of removing potassium-compound between graphite layers surface attachment, places in agate mortar and grinds to form uniform powder, pour into rapidly deionized water, react immediately, thus obtain Graphene in glove box after taking out the potassium-compound between graphite layers of powdery.Final gained Graphene productive rate is 0.45%, and gained Graphene thickness is between 0.9 ~ 6.0nm, and namely the number of plies is between about 1 ~ 17 layer, length and width all between 95 ~ 9500nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.77.
Embodiment 11
A, liquid phase interpolation prepare compound between graphite layers.
Be less than in the glove box of 1ppm in water, oxygen level, highly oriented pyrolytic graphite be cut into the parallelepiped of 1 × 2 × 0.3cm, temperature 400 DEG C, air pressure 10
-3carry out degassed under torr.In 304 Stainless Steel Crucibles (internal diameter 25mm, height 17mm), hold molten lithium, the height of molten lithium is about 15mm, and the temperature of crucible is remained on 350 ± 5 DEG C.Highly oriented pyrolytic graphite bar after degassed end is submerged into 6-8 hour in molten lithium, single order lithium-compound between graphite layers can be obtained.Single order lithium-compound between graphite layers is taken out, to prune while hot the residual lithium wrapped up outside it with stainless steel substrates.
B, prepare Graphene by the compound between graphite layers obtained.
Lithium-compound between graphite layers is placed in agate mortar and grinds to form homogeneous powder, pour into rapidly deionized water take out the lithium-compound between graphite layers of powdery in glove box after, react immediately, thus obtain Graphene.Final gained Graphene productive rate is 0.42%, and gained Graphene thickness is between 0.8 ~ 8.3nm, and namely the number of plies is between about 1 ~ 25 layer, length and width all between 140 ~ 12000nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.75.
Embodiment 12
A, liquid phase interpolation prepare compound between graphite layers.
Be less than in the glove box of 1ppm in water, oxygen fowl amount, highly oriented pyrolytic graphite be cut into the parallelepiped of 1 × 2 × 0.3cm, temperature 400 DEG C, pressure 10
-3carry out degassed under torr.By calcium (purity >=99.99%) and lithium (purity >=99.99%) according to 1: 2 mol ratio add 304 Stainless Steel Crucibles (internal diameter 25mm, height 17mm) in, melting also stirs, and add-on ensures that the height of molten metal is about 15mm.Afterwards the graphite bar after degassed is immersed in liquid metal, and tightly covers crucible cover.At 350 DEG C, be incubated 10 days, take out graphite bar while hot afterwards, scrape off kish above, triple lithium-calcium-compound between graphite layers can be obtained.
B, prepare Graphene by the compound between graphite layers obtained.
Lithium-calcium-compound between graphite layers is placed in agate mortar and grinds to form uniform powder, pour into rapidly deionized water take out the lithium-calcium-compound between graphite layers of powdery in glove box after, react immediately, thus obtain Graphene.Final gained Graphene productive rate is 0.39%, and gained Graphene thickness is between 5.8 ~ 13.6nm, and namely the number of plies is between about 15 ~ 40 layers, length and width all between 130 ~ 6700nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.78.
Embodiment 13
A, molten salt electrolysis of metals legal system are for compound between graphite layers.
Electrolyzer is used as negative electrode (diameter 6mm) with high purity graphite (impurity is less than 35ppm) rod, high purity graphite (impurity is less than 35ppm) crucible (high 140mm, internal diameter 20mm, external diameter 30mm) as anode, melting sodium-chlor is as ionogen.Use one can temperature control vertical heater and be connected with the sealing corundum tubular reactor of water cooling plant.99% pure sodium-chlor is adding in reactor after super-dry, then in reactor, pours into high-purity argon with the speed of 150ml/min, for the gas in purge reactor, keeps the inert atmosphere of reactor in case the generation of oxidation reaction.After continuing to pass into high-purity argon, start to heat up, reach 850 DEG C after about 3 hours, after sodium fusion to be chlorinated, negative electrode is slowly inserted in melting salt.The length inserted in fused salt is remained a constant.Electrolysis is carried out 3 hours afterwards with the continuous current of 5A.After electrolysis terminates, after device cooling, taking-up sealed reactor transfers to water, oxygen level is less than in the glove box of 1ppm, scrapes off sodium-chlor residual on negative electrode, can obtain sodium-compound between graphite layers.
B, prepare Graphene by the compound between graphite layers obtained.
Sodium-compound between graphite layers is placed in agate mortar and grinds to form uniform powder, pour into rapidly deionized water take out the sodium-compound between graphite layers of powdery in glove box after, react immediately, thus obtain Graphene.Final gained Graphene productive rate is 0.39%, and gained Graphene thickness is between 3.8 ~ 9.2nm, and namely the number of plies is between about 10 ~ 27 layers.Length and width all between 150 ~ 6700nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.76.
Embodiment 14
A, two warm area vapor transportation legal systems are for compound between graphite layers.
Natural graphite (diameter < 30 μm) 1.92g and potassium 0.78g is respectively charged into heat-resistant glass tube both sides, vacuumizes, reach about 1.33Pa to vacuum tightness.Heat with two groups of electrothermal ovens, first heated graphite end, after graphite end temperature rises to 450 DEG C, reheat potassium end, and make potassium end temperature maintain 250 DEG C.Now start slowly to reduce graphite end temperature, make it remain on 280 ~ 300 DEG C, heat 3 days, finally obtain bronze spherical product at graphite end, be obtained potassium-compound between graphite layers.Heat-resistant glass tube is transferred to water, oxygen level is less than in the glove box of 1ppm, take out potassium-compound between graphite layers wherein.
B, prepare Graphene by the compound between graphite layers obtained.
Heat-resistant glass tube is transferred to water, oxygen level is less than in the glove box of 1ppm, take out potassium-compound between graphite layers, the retained material of removing potassium-compound between graphite layers surface attachment, place in agate mortar and grind to form homogeneous powder, pour into rapidly deionized water take out the potassium-compound between graphite layers of powdery in glove box after, react immediately, thus obtain Graphene.Final gained Graphene productive rate is 0.45%, and gained Graphene thickness is between 0.8 ~ 6.7nm, and namely the number of plies is between about 1 ~ 20 layer.Length and width all between 110 ~ 6700nm, the ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.79.
Embodiment 15
A, two warm area vapor transportation legal systems are for compound between graphite layers.
Natural graphite (median size: 220 μm) 1.92g and strontium 1.94g is respectively charged into heat-resistant glass tube both sides, vacuumizes, reach about 0.1MPa to vacuum tightness.Heat with two groups of electrothermal ovens, first heated graphite end, after graphite end temperature rises to 600 DEG C, reheat strontium end, and make strontium end temperature maintain 450 DEG C.Now start slowly to reduce graphite end temperature, make it remain on 480 ~ 500 DEG C, heat two weeks, finally obtain the spherical product of reddish-brown at graphite end, be obtained strontium-compound between graphite layers.
B, prepare Graphene by the compound between graphite layers obtained.
Heat-resistant glass tube is transferred to water, oxygen fowl amount is less than in the glove box of 1ppm, take out strontium-compound between graphite layers, the retained material of removing strontium-compound between graphite layers surface attachment, place in agate mortar and grind to form homogeneous powder, pour into rapidly deionized water take out the strontium-compound between graphite layers of powdery in glove box after, react immediately, thus obtain Graphene.Final gained Graphene productive rate is 0.44%, and gained Graphene thickness is between 4.2 ~ 13.8nm, and namely the number of plies is between about 11 ~ 40 layers, length and width all between 80 ~ 7800nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.77.
Embodiment 16
Mechanically peel method is peeled off compound between graphite layers and is prepared Graphene
With the lithium-compound between graphite layers prepared by battery discharge method described in embodiment 5 for raw material, be less than in the glove box of 1ppm in water, oxygen level and get 0.02g lithium-compound between graphite layers powder dispersion in dimethylbenzamide (DMF), stir.Then put into a tetrafluoroethylene bottle together with zirconia ball (diameter 2.0-2.5mm, heavy 200g), tetrafluoroethylene bottle is sealed.Utilize ball mill (use instrument as: QM-3SP2 planetary ball mill (Nanjing Univ. Instrument Factory)) with the rotating speed ball milling 30h of 300rpm.Take out gained dispersion liquid afterwards with 4000rpm, carry out centrifugal 30 minutes, finally obtain the upper strata dispersion liquid containing Graphene.Final gained Graphene productive rate is 0.61%, and gained Graphene thickness is between 0.9 ~ 4.6nm, and namely the number of plies is between about 1 ~ 13 layer, length and width all between 70 ~ 8600nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.75.
Embodiment 17
Electrolytic stripping method is peeled off compound between graphite layers and is prepared Graphene
Electrolyzer is used as negative electrode with the compound between graphite layers electrode that battery discharge method described in embodiment 5 is obtained, high purity graphite (impurity is less than 35ppm) crucible (high 140mm, internal diameter 20mm, external diameter 30mm) as anode, melting lithium chloride is as ionogen.Use one can temperature control vertical heater and be connected with the sealing corundum tubular reactor of water cooling plant.99% pure lithium chloride is adding in reactor after super-dry, then in reactor, pours into high-purity argon with the speed of 150ml/min, for the gas in purge reactor, keeps the inert atmosphere of reactor in case the generation of oxidation reaction.After continuing to pass into high-purity argon, start to heat up, reach 850 DEG C after about 3 hours, after sodium fusion to be chlorinated, negative electrode is slowly inserted in melting salt.Electrolysis is carried out 3 hours afterwards with the continuous current of 10A.After electrolysis terminates, after device cooling, taking-up sealed reactor transfers to water, oxygen level is less than in the glove box of 1ppm, scrapes off sodium-chlor residual on negative electrode, obtains Graphene after negative electrode deionized water being cleaned repeatedly removing impurity.Final gained Graphene productive rate is 0.61%, and gained Graphene thickness is between 4.5 ~ 13nm, and namely the number of plies is between about 12 ~ 38 layers, length and width all between 69 ~ 5400nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.75.
Embodiment 18 ~ 38
Stripper stripping method is peeled off compound between graphite layers and is prepared Graphene
With the lithium-compound between graphite layers prepared by battery discharge method described in embodiment 5 for raw material, lithium-compound between graphite layers powder is dropped in stripper, (use instrument as ultrasonic cleaner (manufacture of Chinese Shanghai Ke Dao ultrasonic instrument company limited) in ultrasonic wave, model: SK2510LHC) under 53Hz environment ultrasonic 30 minutes, under 500rpm rotating speed, (use instrument as flying pigeon board whizzer (manufacture of Chinese Shanghai An Ting scientific instrument factory) afterwards, model: TDL80-2B) centrifugal 90 minutes, obtain Graphene.The present embodiment stripper used is selected from alcohol, ketone, ester, amine, sulfone, chlorobenzene, organic acid, ionic liquid in inorganic acid aqueous solution, water phase surfactant mixture and the organic liquid in aforementioned inorganic liquid.Wherein NMP:1-N-methyl-2-2-pyrrolidone N-, DMF: dimethylbenzamide.
Embodiment 39 ~ 47
Stripper stripping method is peeled off compound between graphite layers and is prepared Graphene.
With the lithium-compound between graphite layers prepared by battery discharge method described in embodiment 5 for raw material, lithium-compound between graphite layers powder is dropped in stripper, (use instrument as ultrasonic cleaner (manufacture of Chinese Shanghai Ke Dao ultrasonic instrument company limited) in 53Hz ultrasonic wave, model: SK2510LHC) under environment ultrasonic 30 minutes, under 500rpm rotating speed, (use instrument as flying pigeon board whizzer (manufacture of Chinese Shanghai An Ting scientific instrument factory) afterwards, model: TDL80-2B) centrifugal 90 minutes, obtain Graphene.The present embodiment stripper used is selected from the mixture of two or more component of aforementioned inorganic liquid and organic liquid.
Embodiment 48
Compound between graphite layers is prepared in A, scorification/solid phase pressurization combination.
Be less than in the glove box of 1ppm in water, oxygen level, graphite (particle diameter 40 ~ 50 μm) 1.44g and potassium (particle diameter 200 ~ 400 μm) 2g is mixed, is placed in tightness system and is forced into 15kbar.Be heated to 200 DEG C afterwards, keep this pressure and temperature 10 hours, cool afterwards.Agate mortar is utilized to be clayed into power by gained solid.
Then in glove box, gained pressed powder is placed in flat 100ml there-necked flask with the potassium 1.9g being cut into irregular bulk together with a stirrer.There-necked flask is sealed, takes out glove box, connect vacuum line, vacuumize, and pass into helium, make bottle internal gas pressure a little more than normal atmosphere.Start heating afterwards, temperature melts completely to potassium when about 100 DEG C, now starts to carry out fiercer stirring.After temperature rises to 150 DEG C be incubated 20 minutes, potassium-compound between graphite layers.
The combination of B, stripper stripping/mechanically peel method is peeled off compound between graphite layers and is prepared Graphene
The retained material on the potassium-compound between graphite layers surface of gained is removed in glove box, getting potassium-compound between graphite layers powder 0.02g drops in dimethylbenzamide (DMF), (use instrument as ultrasonic cleaner (manufacture of Chinese Shanghai Ke Dao ultrasonic instrument company limited) in 53Hz ultrasonic wave, model: SK2510LHC) under environment ultrasonic 40 minutes, afterwards by this dispersion liquid and zirconia ball (diameter 2.0-2.5mm, heavy 200g) put into a tetrafluoroethylene bottle together, tetrafluoroethylene bottle is sealed.Utilize ball mill (use instrument as: QM-3SP2 planetary ball mill (Nanjing Univ. Instrument Factory)) with the rotating speed ball milling 25 hours of 300rpm.Take out gained dispersion liquid afterwards with 4000rpm, carry out centrifugally (using instrument as flying pigeon board whizzer (manufacture of Chinese Shanghai An Ting scientific instrument factory), model: TDL80-2B) 30 minutes, finally obtain the upper strata dispersion liquid containing Graphene.Final gained Graphene productive rate is 0.70%, and gained Graphene thickness is between 0.8 ~ 8.7nm, and namely the number of plies is between about 1 ~ 25 layer, length and width all between 65 ~ 13000nm, the strength ratio I at D peak and G peak in Raman spectrum
d/ I
gvalue is 0.78.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered as in protection scope of the present invention.
Claims (5)
1. a preparation method for Graphene, is characterized in that, take graphite as raw material, obtaining compound between graphite layers, then peeling off described compound between graphite layers and obtaining Graphene by inserting metal in graphite layers;
The preparation method of described compound between graphite layers is battery discharge method;
The method of described stripping compound between graphite layers is that stripper is peeled off;
Described Graphene thickness is 0.3 ~ 15nm, and length and width are between 5 ~ 15000nm;
Described metal is lithium;
The detailed process of described battery discharge method:
By special spherical graphite SSG, acetylene black, polyvinylidene difluoride (PVDF) PVDF in mass ratio 8:1:1 ratio mixing, add 1-Methyl-2-Pyrrolidone NMP and make PVDF concentration within the scope of 0.005-0.03g/mL, stir, furnishing pasty slurry; Its uniform spreading is overlayed on Copper Foil, after solvent evaporates is complete, punch tool is utilized to obtain circular graphitic electrode slice, by the vacuum-drying after 12 hours at 80 DEG C of obtained Graphite Electrodes sheet, select metal lithium sheet as battery cathode, Graphite Electrodes is as anode, lithium hexafluoro phosphate being dissolved in volume ratio is that solution in the EC/EMC/DMC NSC 11801/Methyl ethyl carbonate/methylcarbonate ternary mixed solvent of 1:1:1 is as electrolytic solution, barrier film adopts polypropylene porous film, is less than assembled battery in the glove box of 1ppm in water, oxygen level; Then the battery of assembling is carried out impulsive discharge, after arranging according to parameter given below, can impulsive discharge be carried out: in each circulation, carry out constant-current discharge 5 minutes with the discharge rate of 0.05C, leave standstill 12 minutes, circulate successively; Pulse discharge time is 7 days, then stops electric discharge, disassembles battery, take out the single order lithium-compound between graphite layers of negative pole in the glove box that water, oxygen level are less than 1ppm; After liquid volatilization to be electrolysed, lithium-compound between graphite layers is scraped gently from copper sheet from, place in agate mortar and grind to form uniform powder, pour into rapidly deionized water take out the lithium-compound between graphite layers of powdery in glove box after, described deionized water, as stripper, is peeled off the metallic lithium in lithium-compound between graphite layers and obtained Graphene.
2. the preparation method of Graphene as claimed in claim 1, is characterized in that, described stripper be selected from inorganic liquid and organic liquid one or more.
3. the preparation method of Graphene as claimed in claim 2, it is characterized in that, described inorganic liquid is selected from water or inorganic acid aqueous solution.
4. the preparation method of Graphene as claimed in claim 2, it is characterized in that, described inorganic liquid is water.
5. the preparation method of Graphene as claimed in claim 2, it is characterized in that, described organic liquid is selected from: alcohol, ketone, ester, amine, sulfone, chlorobenzene, organic acid, ionic liquid.
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