CN104264179B

CN104264179B - A kind of method being prepared Graphene by graphite raw ore electrolysis

Info

Publication number: CN104264179B
Application number: CN201410476466.9A
Authority: CN
Inventors: 王俊中; 王俊英; 郭全贵; 闫蕊; 黄建林
Original assignee: Shanxi Institute of Coal Chemistry of CAS
Current assignee: Shanxi Institute of Coal Chemistry of CAS
Priority date: 2014-09-17
Filing date: 2014-09-17
Publication date: 2016-06-22
Anticipated expiration: 2034-09-17
Also published as: CN104264179A

Abstract

A kind of method being prepared Graphene by graphite raw ore electrolysis is by micro crystal graphite crushing raw ore, sieve, fully not broken raw materials recovery utilizes, micro crystal graphite original ore powder or not sufficiently delaminated raw ore are made electrode, the electrolysis in electrolyzer of made electrode, solid-liquid separation, separate the solid obtained to peel off further, obtaining not sufficiently delaminated raw ore, rough Graphene, rough Graphene separating-purifying goes out Graphene。The present invention has with low cost, and preparation process is simple, and device is simple, processing ease, and product quality is good, and process safety is high, the advantage being produced on a large scale。

Description

A kind of method being prepared Graphene by graphite raw ore electrolysis

Technical field

The preparation method that the present invention relates to a kind of Graphene, particularly to a kind of method directly being prepared Graphene by graphite raw ore electrolysis。

Background technology

From 2004, the physics of Univ Manchester UK taught after Geim etc. adopts micromechanics stripping method to prepare and observe single-layer graphene crystal, and namely this new carbon becomes a study hotspot of materialogy, physics and chemical field。Additionally, Graphene has potential using value at numerous areas such as lithium ion battery, ultracapacitor, electrochemical catalysis, sensor, polymer composite, storage material and opto-electronic conversion。

Large-scale low-cost prepares the method for high-quality Graphene, is one of the key of the research of Graphene and application。In recent years, many scholars are devoted to the preparation method exploring single or multiple lift Graphene, the preparation method of the Graphene being currently known mainly has two classes, the stripping method from top to bottom that one class is is raw material with graphite, such as the oxidation-reduction method (such as Hummers method) etc. that mechanical stripping method, graphene oxide convert, another kind of is method from bottom to top to be converted into Graphene through Overheating Treatment for carbon source containing carbon compound, such as chemical vapour deposition technique, SiC vacuum thermal cracking method, epitaxial growth method etc.。Wherein first kind method has abundant advantage with graphite for raw material, because graphite mineral reserve resource reserve is huge on the earth, 70% in China。Graphite oxide reducing process is that current cost is minimum and be easiest to the graphene preparation method accomplished scale production。Graphite oxide reducing process is that with strong acid and Strong oxdiative substance reaction, native graphite is generated graphite oxide (GO), preparing into graphene oxide (mono-layer graphite oxide) through ultrasonic disperse, the oxy radical adding reducing agent removal graphite oxide surface obtains Graphene。Its relative efficiency, but subsequent processing steps is loaded down with trivial details, cost occupy high-leveled and difficult under；Additionally its shortcoming also has in redox process, and the electronic structure of Graphene and perfection of crystal are easily subject to the destruction of strong oxidizer, and then affect the intrinsic property of Graphene。

In the research of international forward position, electrochemical production Graphene attracts wide attention in recent years。In the preparation method that Graphene is numerous, the method is had simple, economical, nothing destructiveness, environmental friendliness, the advantage that can operate at normal temperatures and pressures and can be controlled the number of plies and the surface nature of Graphene by electrode potential when regulating intercalation-stripping, is therefore expected to become the effective way of preparation of industrialization Graphene。Such as (the Adv.Funct.Mater.2008 such as Liu, 18,1518 1525) with ionic liquid 1-octyl group 3-methyl-imidazoles hexafluorophosphate for electrolyte, pure graphite rod is electrode the DC voltage applying 15V between both positive and negative polarity, and graphite anode rod is aoxidized gradually peels off the graphene film obtained with functionalized carbon hydrogen compound。Other is using water system electrolyte or strong acid as electrolyte, as using kayexalate aqueous solution as electrolyte, high purity graphite rod is electrode, adds 5V DC source and peels off and obtain Graphene (Carbon.2009,47,3,242 3246)。Graphene product prepared by above method is adopted all to there is productivity low, the shortcomings such as defect is many, it is impossible to well meet the demand of practical application。(the international patent application no US61/398 such as Wang, 468,2010.06.25,201180036690.0, PCT/SG2011/000225,2011.06.24, J.Am.Chem.Soc.2011,133,8888-8891), ultrasonic using Allyl carbonate lithium ion as intercalating agent combined high-strength, stripping negative electrode graphite obtains productivity and reaches more than 70%, has the Graphene of 1-9 layer。But the method uses expensive lithium salts, cost is high；It addition, the method lacks electrode design, the stability of technique is bad, has short circuit thermal and cause organic solvent burning to produce fire trouble in charging process。Not long ago, applicant is with the electrolyte of organic carbonate and inorganic salt for the intercalation swelling graphite of dispersant electrochemistry, optimize electrode and design of electrolysis cells, (Wang Jun is medium for process stabilizing and safety, " method of the swelling preparing graphite alkene of a kind of electrochemistry ", Chinese Patent Application No.: 201310659172.5), but, the method can not effectively be applicable to crystallite (earthy, amorphous) the graphite raw ore of rich reserves。

Native graphite is different according to its crystallization degree, can be divided into crystalloid (scale) graphite and micro crystal graphite (being called aphanitic graphite or amorphous graphite) two classes。Crystalline flake graphite grade is between 2%～10%, and mean diameter 0.01～3mm, native floatability is better。Being made up of many small graphite crystals in natural micro crystal graphite structure, phosphorus content is 60%～80%, part up to 95%, mean diameter 0.01～1 μm, but floatability is poor, traditional crystalline flake graphite floatation process and inapplicable it。The graphite of natural output is seldom pure, often contains the impurity of 10～20%, including SiO₂、Al₂O₃、MgO、CaO、P₂O₅、CuO、V₂O₅、H₂O、S、FeO_xAnd H, N, CO₂、CH₄、NH₃Deng。At present, the method purifying crystalloid and aphanitic graphite ore deposit both at home and abroad mainly has floatation, high temperature method, alkali acid, hydrogen fluoride and chlorinating roasting etc.。China's aphanitic graphite reserves are big, phosphorus content is high, good conductivity, wide material sources and cheap, and this just makes it possess the inherent advantage realizing Graphene low cost, mass production。But the chemical reagent such as the Fluohydric acid. of the industrial most severe toxicity of micro crystal graphite raw ore purify, and cause serious environmental pollution, and are all simply be processed into the low value-added products such as aquadag。Do not have any directly to prepare into the patent of Graphene, paper and report。

In sum, prepare Graphene at present mainly with pure graphite for raw material, but graphite is to purify out through a lot of steps from graphite raw ore, complex process, seriously polluted。World's micro crystal graphite source of crude is big, and particularly China's reserves (such as Hunan and Inner Mongol etc.) proportion is big, but is not suitable for floatation process, can only make the after-products such as aquadag。Finding no through retrieval utilizes micro crystal graphite raw ore directly to prepare into the patent of Graphene, paper and report。

Summary of the invention

It is an object of the invention to provide a kind of with low cost, preparation process is simple, and device is simple, processing ease, and product quality is good, and process safety is high, the method being prepared Graphene by micro crystal graphite raw ore electrolysis being produced on a large scale。

The main innovation part of the present invention is in that: directly prepare Graphene with micro crystal graphite raw ore one-step method, and purity is high, and productivity is high, and product is not graphite, but Graphene。Next has invented the new technical matters efficiently preparing Graphene for micro crystal graphite raw ore。

The theoretical foundation that the present invention is directly prepared Graphene technique by micro crystal graphite raw ore one-step method is clear and definite:, good conductivity high according to the phosphorus content of micro crystal graphite raw ore and can the electrochemical principle of ion insertion and directly prepare Graphene；The separation and Extraction Graphene according to the conductivity difference of material with carbon element and mineral and density, the physical and chemical principle of dissolubility difference, on the basis of these two theoretical foundations, laboratory practices proposes the principle model of micro crystal graphite raw ore electrochemical intercalation-leafing-separation, and realizes technological process prepared by Graphene。

The present invention is by the following technical solutions:

Micro crystal graphite raw ore is carried out crushing and uses flexibly with the method such as discharge and recharge and electrode fabrication assembling。As the micro crystal graphite original ore powder after crushing makes porous electrode and the electrod-array of good conductivity；Can binder free when making electrode, it is also possible to add binding agent；Then with unique liquid for electrolyte, adopting sequencing charge and discharge system, positive pole (anode) and negative pole (negative electrode) two class electrode can be peeled off simultaneously；Electrode after electrolysis is peeled off further, including solvent dispersion, and ultrasonic/stirring, centrifugal/sucking filtration, washing dried, it is thus achieved that defect is few, the Graphene of high crystallization, and part intercalator and electrolyte liquid-phase system and not sufficiently delaminated raw ore can be recycled。In order to avoid short circuit, with the polymeric bag of porous insulation or intermembranous every anode with negative electrode, electrolyte free-flow can be allowed, can prevent again anode from directly contacting with negative electrode。

The technical scheme that the present invention is concrete comprises the following steps:

(1), by micro crystal graphite crushing raw ore, sieving, fully not broken raw materials recovery utilizes；(2), micro crystal graphite original ore powder or not sufficiently delaminated raw ore are made electrode；(3), the electrolysis in electrolyzer of made electrode, solid-liquid separation；(4), separate the solid that obtains and peel off further, obtain not sufficiently delaminated raw ore, rough Graphene；(5), rough Graphene separating-purifying goes out Graphene。

One, step (1) concrete technology includes as follows:

Crushing including but not limited to Mechanical Crushing, ultrasonic grinding method of procedure described above (1) micro crystal graphite raw ore；After broken, the particle diameter of micro crystal graphite raw ore is at 10 nanometers to 5 millimeters (10nm-5mm)；Shattering process can add dispersant, it is also possible to be not added with dispersant。

Described Mechanical Crushing including but not limited to ball milling, ultrasonic grinding etc. therein more than one；Ball milling ball can be the one therein such as stainless steel ball, agate ball, zirconia ball, alumina balls or carborundum ball；The diameter of ball is 3 millimeters to 15 millimeters (3-15mm)；The material of ball grinder can be rustless steel, Achates or zirconium oxide；Ratio of grinding media to material (mass ratio) is 15-150:1；Rotational speed of ball-mill is: 50 revs/min to 580 revs/min (50-580rpm)；Gas is more than one in air, nitrogen, argon or helium；Ball-milling Time is 0.5 hour to 72 hours (0.5-72h)；

Frequency 20 KHz ultrasonic during described ultrasonic grinding is to 30 KHz (20-30KHz), power density 500 watts to 1000 watts (500-1000w), 10 minutes to the 30 hours time (10min-30h), temperature 20 degrees Celsius to 60 degrees Celsius (20-60 DEG C)。

Described dispersant is including but not limited to organic solvent, mineral acid (dense or rare), soluble inorganic aqueous alkali, the organic solution of soluble inorganic salt or aqueous solution。The ratio of dispersant (volume, milliliter) and micro crystal graphite raw ore (quality, gram) controls between 1 ml/g to 100 ml/g (1-100ml/g)。

Described organic solvent can including but not limited to N-Methyl pyrrolidone, N, dinethylformamide, N, N-dimethyl acetylamide, N-METHYLFORMAMIDE, dimethyl sulfoxide, benzene,toluene,xylene, chloroform, dichloromethane, ethanol, isopropanol, acetone, acetonitrile, cyclic carbonate (such as Allyl carbonate) or linear carbonate are (such as ethylene carbonate, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate) in one。

Described mineral acid (dense or rare) is including but not limited to H₂SO₄、H₃PO₄、HNO₃、HClO₄、HClO₃One in S。

Described mineral acid (dense or rare) mass concentration is between 1% to 98% (1-98%)。

Described soluble inorganic alkali is including but not limited to NaOH, KOH, NH₃·H₂O、Na₂CO₃、K₂CO₃In one。

The mass concentration of described soluble inorganic aqueous alkali is between 0.5% to 20% (0.5-20%)。

Described soluble inorganic salt is including but not limited to perchlorate, sulfate, nitrate, phosphate, LiPF₆、LiAsF₆、LiBF₄, one in LiCl。

The mass concentration of described soluble inorganic saline solution is between 0.01% to 15% (0.01-15%)。

The mass concentration of described soluble inorganic salt organic solution is between 0.01% to 10% (0.01-10%)。

Two, step (2) concrete technology includes as follows:

Micro crystal graphite original ore powder is made as mentioned above electrode include micro crystal graphite breeze or not sufficiently delaminated raw ore to suppress to form shaped electrode, it is also possible to be directly placed in polymer pouches using the micro crystal graphite original ore powder after broken or not sufficiently delaminated raw ore and use as electrode。It is 1-50 MPa (1-50MPa) that micro crystal graphite original ore powder or the compacting of not sufficiently delaminated raw ore form pressure used during shaped electrode, and, press temperature can be preferably 0 degree Celsius to 400 degrees Celsius (0-400 DEG C)；And compressing electrode is including but not limited to membranaceous, circle or side column；Binding agent can be added, it is also possible to be added without binding agent during electrode pressing。Anode electrode and cathode electrode all contain the graphite content of mass fraction more than 50%, and its resistivity, less than 1 kilo-ohm of momme (1K Ω m), has hole, and specific surface area is more than every gram of (2m of 2 square meter²/g)。

Compressing electrode can be self-supporting, it is also possible to add supporter。The supporter adopted can be selected from including but not limited to one therein such as platinum, gold, silver, copper, copper alloy, titanium, titanium alloy, graphite, Lead oxide brown。Can at supporter while compacting on micro crystal graphite original ore powder or not sufficiently delaminated raw ore, it is also possible to suppress micro crystal graphite original ore powder or not sufficiently delaminated raw ore on both sides simultaneously。The micro crystal graphite original ore powder suppressed on supporter or the thickness preferably 1 millimeter to 5 millimeters (1-5mm) of not sufficiently delaminated raw ore。The binding agent that electrode pressing adopts is selected from including but not limited to the one in polyvinyl alcohol (PVA), polyoxyethylene ether, politef (PTFE), sodium carboxymethyl cellulose (CMC), carboxymethyl cellulose, Kynoar (PVDF), polyurethane, resin, Colophonium。Ratio between the gross mass (gram) of the quality (gram) of binding agent and micro crystal graphite original ore powder or not sufficiently delaminated raw ore controls between 0.01 gram gram to 0.25 gram gram (0.01g/g-0.25g/g)。

The thickness of the columnar electrode that self-supporting compressing as above is membranaceous or square is 1 millimeter to 5 millimeters (1-5mm) preferably, the diameter preferably 1 millimeter to 5 millimeters (1-5mm) of the columnar electrode of self-supporting circle, the binding agent that electrode pressing adopts is selected from including but not limited to the one in polyvinyl alcohol (PVA), polyoxyethylene ether, politef (PTFE), sodium carboxymethyl cellulose (CMC), carboxymethyl cellulose, Kynoar (PVDF), polyurethane, resin, Colophonium。Ratio between the gross mass (gram) of the quality (gram) of binding agent and micro crystal graphite original ore powder or not sufficiently delaminated raw ore controls between 0.01 gram gram to 0.25 gram gram (0.01g/g-0.25g/g)。

Three, step (3) concrete technology includes as follows:

The electrod-array that electrolyzer as above forms including, but not limited to multiple electrodes, multiple electrolyzers form cell array again。Each electrolyzer can independently be powered by single power supply, it is also possible to is together in parallel and is powered by single power supply。Multiple electrolyzers are likely to need multiple power supply to power。Power supply can be DC source can also be the alternating current power supply of frequency modulation。Multiple electrolyzers are prone to structure, it is simple to upgrading expanding production。The spacing of anode electrode and cathode electrode is between 1 millimeter to 50 millimeter (1-50mm), use between anode electrode and cathode electrode including, but not limited to porous insulation polymer (such as polypropylene) bag or intermembranous every, the average pore size of porous polymer bag or film is between 0.2 micron to 20 micron (0.2-20 μm)。

4 volts of direct currents to 10 volts (4-10V) or alternating voltage is applied between the method Anodic described above and negative electrode；Each electrolysis time is between 2 hours to 144 hours (2-144h), the time of conversion charging current or voltage direction, electrolysis temperature was between 20 degrees Celsius to 60 degrees Celsius (20-60 DEG C) between 10 seconds to 12 hours (10s-12h)；Electrolyte can adopt aqueous electrolyte or non-aqueous electrolyte；The ratio of electrolyte (volume, milliliter) and electrode (quality, gram) controls between 1 ml/g to 100 ml/g (1-100ml/g)。

Polar solvent in electrolyte, solvated ion, electrolyte ion, electrochemical reaction product etc. therein more than one under the effect of voltage and current can intercalation in electrode atom interlayer。In electrolytic process, can there is chemical reaction in ion and solvent, generates new product at electrode atom interlayer。This product can be gaseous state, it is also possible to be solid-state。They can stop the recovery of graphite state。The solid phase interface phase (SEI) of electrode surface has variform, and such as vesicle shape and graininess, but they can be removed by subsequent treatment。

In the method described above in appropriate design the electrode sequence that assembles, each electrode can obtain electrolysis leafing in charge and discharge process, sequencing discharge and recharge had both made electrode by sufficient electrolysis, the abundant intercalation of intercalator is in the atom interlayer of electrode, side reaction is effectively suppressed, and in turn ensure that the safety of cell reaction。The temperature of whole electrolysis system is controlled between 20 degrees Celsius to 60 degrees Celsius (20-60 DEG C), and safety and the effectiveness of reaction are further strengthened。The electrolyte molecule of polarization and charged ion enter the atom interlayer of electrode under curtage drives, but electric charge changes, chemical reaction is occurred to be trapped in electrode atom interlayer, or generate solid phase interface phase (SEI) or produce gas simultaneously, form air pressure and duct, it is simple to being further inserted into and electrode sufficiently delaminated of liquid flowing and intercalator。

Electric current density can by the output voltage control of the resistance of electrolyzer system and power supply, it is also possible to being controlled by power supply itself, the ratio of electrode quality can be regulated and controled by electric current density and charge volume。The rising of electrolysis temperature is conducive to ion flow, accelerates electrolysis effectiveness。But the too high meeting of temperature causes fire trouble, brings safety problem, so temperature controls below 60 DEG C。

Described aqueous electrolyte is including but not limited to HCl, HNO₃、H₂SO₄、HClO₄、HClO₃S, NaOH aqueous solution, KOH aqueous solution, Na₂CO₃Aqueous solution, K₂CO₃Aqueous solution, soluble sulphate aqueous solution, soluble nitrate aqueous solution, soluble phosphoric acid saline solution, solubility perchlorate aqueous solution；In aqueous solution, the concentration of solute is between 0.01 mg/ml to 300 mg/ml (0.01-300mg/ml)。

The electrolyte of described non-water system is including but not limited to hydrophilic glyoxaline ion liquid, hydrophilic pyridine ionic liquid, hydrophilic pyrrole ionic liquid, cyclic carbonate electrolyte, linear carbonate electrolyte, the one in the mixed electrolytic solution of cyclic carbonate and linear carbonate composition。

Described hydrophilic glyoxaline ion liquid, hydrophilic pyridine ionic liquid, hydrophilic pyrrole ionic liquid are including but not limited to pure glyoxaline ion liquid, pure pyridine class ionic liquid, pure pyrrole ionic liquid, one in the mixture of glyoxaline ion liquid, pyridine ionic liquid or pyrrole ionic liquid and water composition, the weight/mass percentage composition of water is between 0.001% to 20% (0.001-20%)。

Solvent in the mixed electrolytic solution of described cyclic carbonate electrolyte, linear carbonate electrolyte, cyclic carbonate and linear carbonate composition can including but not limited to the one in dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethylene carbonate, Allyl carbonate；Solute can including but not limited to LiClO₄、LiPF₆、LiAsF₆、LiBF₄、NaClO₄、LiCl、MgClO₄、KClO₄、NH₄ClO₄、NaNO₃、KNO₃、Al(NO₃)₃、Mg(NO₃)₂、Zn(NO₃)₂In one。The weight/mass percentage composition of solute is (0.01-30%) between 0.01% to 30%, and comprises the water of mass percent 0.01% to 10% (0.01-10%) in electrolyte。

Glyoxaline ion liquid as above is including but not limited to iodate 1,3-methylimidazole, 1,3-methylimidazole Methylsulfate salt, 1,3-methylimidazole dimethyl phosphate salt, 1,3-methylimidazole tetrafluoroborate, 1,3-methylimidazole fluoroform sulphonate, 1,3-methylimidazole perchlorate, 1,3-methylimidazole nitrate, 1,3-methylimidazole mesylate, 1,3-methylimidazole tosilate, 1-ethyl-3-methyllimidazolium bromide, iodate 1-ethyl-3-methylimidazole, iodate 1-vinyl-3-Methylimidazole., bromination 1-vinyl-3-Methylimidazole., 1-vinyl-3-Methylimidazole. perchlorate, 1-vinyl-3-methylimidazolium nitrate, 1-vinyl-3-N-Methylimidazoleacetic salt, 1-vinyl-3-Methylimidazole. tosilate, 1-vinyl-3-methyl imidazolium tetrafluoroborate, 1-propyl group-3-Methylimidazole. perchlorate, 1-propyl group-3-methyl imidazolium tetrafluoroborate, 1-propyl group-3-methylimidazolium nitrate, 1-propyl group-3-N-Methylimidazoleacetic salt, one in 1-propyl group-3-Methylimidazole. tosilate；Hydrophilic pyridine ionic liquid is including but not limited to bromination N-ethylpyridine, ethiodide pyridine, N-ethylpyridine tetrafluoroborate, N-ethylpyridine four fluorophosphate, N-butylpyridinium Chloride, bromination N-butyl-pyridinium, N-butyl-pyridinium tetrafluoroborate, N-butyl-pyridinium mesylate, chlorination N-butyl-3-picoline, bromination N-butyl-3-picoline, one in N-butyl-3-picoline tetrafluoroborate, hydrophilic pyrrole ionic liquid is including but not limited to chlorination N-methyl, butyl pyrrolidine, ethanaminium, N-methvl, butyl pyrrolidine, N-methyl, butyl pyrrolidine fluoroform sulphonate, N-methyl, butyl pyrrolidine mesylate, N-methyl, butyl pyrrolidine tetrafluoroborate, ethanaminium, N-methvl, propyl pyrrole alkane, ethanaminium, N-methvl, ethyl pyrrolidine, N-methyl, ethyl pyrrolidine mesylate, 1-normal-butyl-1-crassitude two (trimethyl fluoride sulfonyl) acid imide, one in N-butyl-pyridinium tetrafluoroborate。

In the method described above, the solid-liquid separation of electrolysis rear electrode and electrolyte uses including, but not limited to average pore size porous polymer (such as polypropylene, polyethylene, polystyrene, polyester and the cellulose) bag of (0.2-20 μm) or film between 0.2 micron to 20 micron。Porous polymer bag is conducive to solid-liquor separation, solid to stay in bag, and liquid is thrown out of, extrudes, extrudes or flows out。

Four, step (4) concrete technology includes as follows:

The peeling off further of electrode described above include utilizing in the methods such as ultrasonic/stirring more than one make electrolysis after electrode peel off further；Adopt centrifugal method to realize solid-liquid separation, obtain not sufficiently delaminated raw ore and rough Graphene。If using aqueous electrolyte, hydrophilic glyoxaline ion liquid electrolyte, hydrophilic pyridine ionic liquid electrolyte or hydrophilic pyrrole ionic liquid electrolyte electrolysis electrode, then peeling off the solvent used further can be water or the aqueous solution containing surfactant, and solid concentration in water or the aqueous solution containing surfactant is between 0.01 mg/ml to 20 mg/ml (0.01-20mg/ml)；If using the electrolyte electrolysis electrode containing ring-type or linear carbonate, then peeling off the solvent used further can be organic solvent, and solid concentration in organic solvent is between 0.01 mg/ml to 20 mg/ml (0.01-20mg/ml)。

Described surfactant can including but not limited to the one in polyvinylpyrrolidone, polyoxyethylene laurel ether, Tween 80, triton X-100, PluronicP123, PluronicF127, PluronicF68, dodecylbenzene sodium sulfonate, Dodecyl trimethyl ammonium chloride, sodium lauryl sulphate, stearic acid, oleic acid, lauric acid, cetyl trimethylammonium bromide, tetrabutyl ammonium bromide, 4 bromide。

The concentration of described aqueous surfactant solution is between 0.0001 mol/L to 0.5 mol/L (0.0001-0.5mol/L)。

Described organic solvent is including but not limited to using ethanol, isopropanol, acetone, chloroform, carbon tetrachloride, oxolane, paracide, N, one in dinethylformamide, DMAC N,N' dimethyl acetamide, methylformamide, methylacetamide, methyl propanamide, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, dimethyl sulfoxide, benzene,toluene,xylene, dichloromethane, acetonitrile, cyclic carbonate, linear carbonate。

Described ring-type is or/and linear carbonate can including but not limited to the one in Allyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, Ethyl methyl carbonate。

Described stirring adopts magnetic force or/mechanical agitation, and the time is 3 hours to 60 hours (3-60h), whipping temp 20 degrees Celsius to 60 degrees Celsius (20-60 DEG C)。

When described solid product is peeled off further, the frequency of sonic oscillation is 5 KHz to 30 KHz (5-30KHz), power density 100 watts to 1000 watts (100-1000w), 2 minutes to the 10 hours time (2min-10h), temperature 20 degrees Celsius to 60 degrees Celsius (20-60 DEG C)；Suspension after ultrasonic is centrifugal 5 minutes to 30 minutes (5-30min) under the rotating speed of 500 revs/min to 3000 revs/min (500-3000rpm)；

Five, step (5) concrete technology includes as follows:

The separating-purifying of Graphene described above is including but not limited to four steps: (1) by rough graphene dispersion in a suitable solvent, adopt in the methods such as ultrasonic/stirring more than one and utilize rough Graphene tentatively to realize separating of Graphene and solid impurity with impurity density, dissolubility and capillary difference；(2) solid that step (1) is prepared alkalescence (such as NaOH, NH₃·H₂O aqueous solution) solution washing removing surface solid phase impurity；(3) solid product after alkali cleaning is neutralized with acid (such as HCl/water solution) aqueous solution washing, and utilize hydrion to replace other non-carbon ion (such as sodium ion) of remnants further；(4) by the solid matter with deionized water after alkali cleaning, pickling or pure water。Then adopting the methods such as centrifugal, sucking filtration/filter pressing to realize solid-liquid separation, gained solid is further dried and obtains graphene powder。Solid concentration in liquid in step (1), (2), (3) and (4) is controlled between 0.01 mg/ml to 300 mg/ml (0.01-300mg/ml) by Graphene (with carbon Mass Calculation)。

In step (1), (2), (3) and (4), the liquid of separating-purifying and washing can be recovered and recycle。

In the method described above, the organic solvent of separating-purifying is including but not limited to using oxolane, tetramethylurea, Methanamide, N-METHYLFORMAMIDE, N, dinethylformamide, acetamide, N-methylacetamide, N, N-dimethyl acetylamide, N-methyl propanamide, 2-Pyrrolidone, N-Methyl pyrrolidone, pyrroles, pyridine, the one in 2-picoline, 3-picoline, 4-picoline。

During described washed product separating-purifying, the frequency of sonic oscillation is 5 KHz to 30 KHz (5-30KHz), power density 100 watts to 1000 watts (100-1000w), 2 minutes to the 10 hours time (2min-10h), temperature 20 degrees Celsius to 60 degrees Celsius (20-60 DEG C)；Suspension after ultrasonic is centrifugal 5 minutes to 30 minutes (5-30min) under 1000 revs/min to 10000 revs/min of (1000-10000rpm) rotating speeds；

As mentioned above centrifugal, sucking filtration or filter pressing are including but not limited to using average pore size porous polymer (such as polypropylene, polyethylene, polystyrene, polyester and the cellulose) bag of (0.2-20 μm) or film between 0.2 micron to 20 micron。Porous polymer bag is conducive to solid-liquor separation, solid to stay in bag, and liquid is thrown out of, extrudes, extrudes or flows out。

The Graphene solid obtained in the method described above can adopt-50 degrees Celsius of (-50 DEG C) lyophilizations, and drying time is 10 hours to 96 hours (10-96h), can obtain the graphene powder presenting metallochrome；Adopting air blast or vacuum drying, temperature is 70 degrees Celsius to 120 degrees Celsius (70-120 DEG C), and drying time is 2 hours to 96 hours (2-96h)；The graphene powder presenting metallochrome can be obtained。

The liquid of technical solution of the present invention mainly has four classes, one class is dispersion liquid is that electrolyte is for electrolysis electrode for pulverizing micro crystal graphite raw ore Equations of The Second Kind, 3rd class I liquid I is for the further stripping of electrode, 4th class I liquid I is for the separating-purifying of rough Graphene, and four class I liquid Is all have the common trait of conduction and polarity。When electrolyte is aqueous electrolyte or water soluble ion liquid, above four class I liquid Is are controlled within the scope dissolved each other, and are conducive to recycling；When electrolyte is containing ring-type or/and during the organic system electrolyte of linear carbonate, above four class I liquid Is are controlled within the scope dissolved each other, and are conducive to recycling。

During the electrochemical stripping of the micro crystal graphite raw ore of technical solution of the present invention or its not sufficiently delaminated product, the electrode in each electrod-array of each electrolyzer can by intercalation-leafing。

The electrochemical stripping of the micro crystal graphite raw ore of technical solution of the present invention or its not sufficiently delaminated product including but not limited to product graphene layer spacing in its microstructure more than micro crystal graphite raw ore interlamellar spacing。

The electrochemical stripping of the micro crystal graphite raw ore of technical solution of the present invention or its not sufficiently delaminated product including but not limited to graphene layer spacing in its microstructure more than 0.340nm。

The electrochemical stripping of the micro crystal graphite raw ore of technical solution of the present invention or its not sufficiently delaminated product including but not limited to electrolyte intercalation in the atom interlayer of micro crystal graphite raw ore or its not sufficiently delaminated product。

The electrochemical stripping of the micro crystal graphite raw ore of technical solution of the present invention or its not sufficiently delaminated product including but not limited to the solute of solvation and the ion insertion of solvation in the atom interlayer of micro crystal graphite raw ore or its not sufficiently delaminated product。

The electrochemical stripping of the micro crystal graphite raw ore of technical solution of the present invention or its not sufficiently delaminated product including but not limited to the solute of solvation and the solvent of solvation and electrochemical reaction product intercalation thereof in the atom interlayer of micro crystal graphite raw ore or its not sufficiently delaminated product。

Including but not limited to electrolyte and electrochemical reaction product thereof in the intercalation compound of the micro crystal graphite raw ore of technical solution of the present invention or its not sufficiently delaminated product, its composition can be liquid, solid-state or gaseous state。

The intercalation compound composition of technical solution of the present invention including but not limited to chlorine element, oxygen element, protium, carbon, nitrogen element, sodium element, element silicon, P elements, potassium element and aluminium element etc. therein more than one。

The intercalation compound composition of technical solution of the present invention is including but not limited to ion, such as perchlorate, sulfate ion, ammonium radical ion, it is also possible to including but not limited to the one therein such as ion of sodium ion, aluminium ion, nitrate ion, phosphate anion, the ion of carbonate solvent, the ion of ion liquid solvent and aqueous solvent。

The intercalation compound composition of technical solution of the present invention including but not limited to electrolyte, solid phase interface phase (SEI), gas, hydrocarbon oxygen compound, solvated ion etc. therein more than one。

The Graphene that in technical solution of the present invention, defect is few including but not limited to Graphene productivity more than 80% (i.e. Graphene product to the ratio of graphite in micro crystal graphite raw ore raw material more than 80%), the phosphorus content of Graphene more than 98%, the Graphene that defect is few also comprise draw together but be not limited to more than 80% the Graphene that the Graphene number of plies is 1-4 atomic layer。

Prepared graphene powder supersound process in various solvents, obtains such as the dispersion of prepared Chinese ink shape, and therefore graphene conductive ink is easy to be produced out。Graphene conductive ink has good printing performance, various pattern can be printed as or brush into high connductivity thin film, the electric conductivity of the graphene film that about 20 microns (20 μm) are thick can reach 10 ohm meters (10 Ω m), it can be seen that the height of the quality of Graphene。

By the statistical analysis of Graphene product and a large amount of sample of micro crystal graphite raw ore raw material is shown, the intensity at (002) peak of the Graphene that different electrolytes system prepares relative to the strength ratio of micro crystal graphite raw ore between 0.1%-3%, this also illustrates micro crystal graphite raw ore layer structure and be destroyed the lack of alignment obtaining Graphene, the productivity of Graphene (i.e. Graphene product to the ratio of graphite in micro crystal graphite raw ore raw material more than 80%) more than 80%。

The SEM photograph of this technique micro crystal graphite raw ore used typical and prepared Graphene product see (Fig. 2 a, b)。Graphene is mainly based on aggregation, and Graphene monolithic size only has hundreds of nanometer, highly uniform, also thinner than ultrathin carbon films。Further statistical analysis through TEM and Raman spectrum shows, Graphene accounts for the overwhelming majority with 1-4 layer, and its weight/mass percentage composition accounts for more than the 80% of Graphene product gross mass。Graphene aggregation in this technique refers to a kind of state that Graphene is assembled。The full analysis of spectrum of the x-ray photoelectron power spectrum (XPS) of micro crystal graphite raw ore and Graphene end product as (Fig. 2 c, d)。It can be seen that in micro crystal graphite raw ore except containing C, O element, possibly together with elements such as Si, Al, Cl。Additionally, C/O atom (C/O=45) ratio is far above C/O atomic ratio (C/O=6) in micro crystal graphite raw ore in Graphene product, it is believed that oxygen mostlys come from Graphene to the absorption of oxygen in air。XPS comparative analysis demonstrates that the purity of prepared Graphene is high, defect is few, non-oxidation。Surface solid impurity as above can separate clean with Graphene。TG and infrared spectrogram (Fig. 2 e from micro crystal graphite raw ore Yu Graphene, f) upper it can be seen that the phosphorus content (> 98wt% of afterproduct Graphene of purification) it is significantly improved than the phosphorus content (80-90wt%) of micro crystal graphite raw ore。After repeatedly washing, product Graphene is not detected by obvious organo-functional group and has existed, illustrated that washing methods of the present invention can effectively remove byproduct of reaction, it is achieved in product Graphene and micro crystal graphite raw ore, impurity has efficiently separated。

Raman (Raman) spectrum is the powerful characterizing Graphene quality。Raman (Raman) spectrogram of typical Graphene is shown in Fig. 3。(Dband, position is at 1342cm at D peak^-1Near) very weak, G peak position is at 1572cm^-1Near, D peak is nearly 1 order of magnitude lower than Graphene prepared by Hummers method with the strength ratio at G peak。To 2D peak, (position is at 2694cm^-1Near) matching then show that Graphene thickness is 1-3 atomic layer (Fig. 3 b)。

Fig. 4 gives typical Graphene TEM photo and electron diffraction pattern pattern analysis, and Graphene is the Graphene of high crystallization, it was shown that the sp of Graphene²The crystal structure of chemical bond is intact, i.e. sp²Carbon crystal layer be saved, defect is few。6 bright spots of internal layer are suitable with the mean flow rate of 6 bright spots of time internal layer, and explanation is 1-4 layer, the Graphene of high crystallization。

The few Graphene of defect in the method described above also including but not limited to some layer graphenes of perchlorate's intercalation, some layer graphenes of sulfate radical intercalation, some layer graphenes of nitrate anion intercalation, phosphate radical intercalation some layer graphenes。

The present invention compared with prior art has the advantage that

1, adopting graphene powder prepared by this technique can be compacted (10-15 atmospheric pressure), resistance is measured less than 2.0 ohm with double; two electrical measurement four-point probe, its electric conductivity 1-2 order of magnitude higher than Graphene prepared by Hummers method。

2, this technique major part dispersant, solvent and electrolyte can be repeatedly circulated, and cost is low。

3, this technique preparation process step is simple, and efficiency is high, and energy consumption is low, and can accomplish scale production。

4, the Graphene quality that prepared by this technique is good, and defect is few, good conductivity。

5, present invention achieves the application in lithium ion battery, electrode material for super capacitor of the Graphene product, charge-discharge velocity is fast, and Graphene is also expected to be applied to the fields such as conductive ink, polymeric additive and heat management simultaneously。

6, this technique prepares the micro crystal graphite raw ore raw material rich reserves of Graphene, cheap and easy to get。

Accompanying drawing explanation

Fig. 1. electrode that (a) micro crystal graphite raw ore is made and the schematic diagram of electrolysis bath, (b) electrolyte intercalation is in the schematic diagram of micro crystal graphite raw ore atom interlayer。

Fig. 2. the SEM photograph of (a) micro crystal graphite raw ore, the SEM photograph of (b) Graphene, the light ray electron spectrum wide range of (c) micro crystal graphite raw ore and Graphene, the carbon C1s spectrum of the x-ray photoelectron power spectrum of (d) micro crystal graphite raw ore and Graphene, (e) micro crystal graphite raw ore and Graphene thermal multigraph (in air atmosphere), the infrared spectrogram of (f) micro crystal graphite raw ore and Graphene。

Fig. 3. the Raman spectrogram of (a) micro crystal graphite raw ore and Graphene (1-3 layer), 2D wave band figure and 1-3 layer fitting data figure thereof in the Raman spectrogram of (b) micro crystal graphite raw ore and Graphene。

The transmission electron microscope picture of Fig. 4 .1-4 layer graphene: (a) low power TEM photo, (b) high power single-layer graphene, (c) high power two layer graphene, (d) high power 3-4 layer graphene, the electron diffraction pattern of (e) single-layer graphene, the electron diffraction pattern of (f) two layer graphene, the electron diffraction pattern of (g) 3-4 layer graphene。

Detailed description of the invention

Embodiment 1:

(1) by the agate ball abrading-ball that 50.0g diameter is 1-1.3cm, ball grinder, in argon shield lower seal to agate jar, is then placed on planetary ball mill and with the rotating speed ball milling 2 hours of 580rpm by 1.0g micro crystal graphite raw ore and 80ml dispersant。With tweezers, agate ball is taken out。Dispersant is 70wt%HClO₄The ratio of aqueous solution, dispersant and micro crystal graphite raw ore raw material is 80ml/g。After ball milling, the mean diameter of micro crystal graphite raw ore is at 30 μm。(2) the micro crystal graphite original ore powder after ball milling is directly loadable in Polythene Bag, makes anode and negative electrode。Distance between anode and negative electrode is 5mm, and the average pore size of Polythene Bag is 0.2 μm。(3) applying the DC voltage of+5V to-5V, electrolysis 120h between the anode and cathode, exchange one-time electrode every 10h, electrolysis temperature controls at 25 DEG C。Electrolyte is the LiClO of 10mg/ml₄Aqueous solution。Electrolyte is 10ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 10 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is thrown out of。(4) solid that solid-liquid separation obtains is dispersed in deionized water for ultrasonic。Supersonic frequency is the frequency of 5KHz, and power density is 100w, time 10h, temperature 25 DEG C。Solid concentration in deionized water is 0.1mg/ml。Then the centrifugal 30min of rotating speed adopting 1000rpm obtains rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) rough graphene dispersion is ultrasonic in deionized water。Supersonic frequency is 5KHz, and power density is 100w, time 10h, ultrasonic temperature 20 DEG C。Suspension after ultrasonic is centrifuged 30min under the rotating speed of 1000rpm。The centrifugal solid obtained uses alkalescence (NaOH of 0.01mol/L) washing, acid (HCl of 0.005mol/L) washing and deionized water to wash 6 times respectively successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is for 0.1mg/ml。Then adopt polypropylene screen (0.5 μm of aperture) sucking filtration, 100 DEG C of dry 24h, collect Graphene sample。The productivity 81% of Graphene, phosphorus content more than 99% (XPS detection), Graphene number of plies 1-4 atomic layer (comprehensive detection) of 85% in sample。

Embodiment 2:

(1) by the agate ball abrading-ball that 50.0g diameter is 1-1.3cm, ball grinder, in argon shield lower seal to agate jar, is then placed on planetary ball mill and with the rotating speed ball milling 2 hours of 580rpm by 1.0g micro crystal graphite raw ore and 80ml dispersant。With tweezers, agate ball is taken out。Dispersant is 10wt%H₂SO₄The ratio of aqueous solution, dispersant and micro crystal graphite raw ore raw material is 80ml/g。After ball milling, the mean diameter of micro crystal graphite raw ore is at 30 μm。(2) the micro crystal graphite original ore powder after ball milling is directly loadable in Polythene Bag, makes anode and negative electrode。Distance between anode and negative electrode is 5mm, and the average pore size of Polythene Bag is 0.2 μm。(3) applying the DC voltage of+8V to-8V, electrolysis 60h between the anode and cathode, exchange one-time electrode every 3h, electrolysis temperature controls at 40 DEG C。Electrolyte is the H of 100mg/ml₂SO₄Aqueous solution。Electrolyte is 100ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 0.2 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is extruded。(4) solid that solid-liquid separation obtains is dispersed in deionized water for ultrasonic。Supersonic frequency is 10KHz, and power density is 300w, time 3h, temperature 40 DEG C。Solid concentration in deionized water is 5mg/ml。Then the centrifugal 5min of rotating speed adopting 3000rpm obtains rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) rough graphene dispersion is ultrasonic in deionized water。Supersonic frequency is 15KHz, and power density is 500w, time 25min, temperature 40 DEG C。Suspension after ultrasonic is centrifuged 20min under the rotating speed of 7000rpm。The centrifugal solid obtained uses alkalescence (the NaOH aqueous solution of pH=11) washing, acid (the HCl/water solution of pH=4) washing and deionized water respectively to wash 6 times successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is at 10mg/ml。Then adopt polyethylene (15 μm of aperture) bag filter pressing, lyophilization 60h, collect Graphene sample。After testing, the productivity of Graphene is more than 84%, and phosphorus content is more than 99% (XPS detection), and in sample, the Graphene number of plies of more than 87% is 1-4 layer (comprehensive detection)。

Embodiment 3:

(1) by the agate ball abrading-ball that 50.0g diameter is 1-1.3cm, ball grinder, in argon shield lower seal to agate jar, is then placed on planetary ball mill and with the rotating speed ball milling 2 hours of 580rpm by 1.0g micro crystal graphite raw ore and 80ml dispersant。With tweezers, agate ball is taken out。Dispersant is 35wt%HNO₃The ratio of aqueous solution, dispersant and micro crystal graphite raw ore raw material is 80ml/g。After ball milling, the mean diameter of micro crystal graphite raw ore is at 30 μm。(2) the micro crystal graphite original ore powder after ball milling is directly loadable in Polythene Bag, makes anode and negative electrode。Distance between anode and negative electrode is 5mm, and the average pore size of Polythene Bag is 0.2 μm。(3) applying the DC voltage of+10V to-10V, electrolysis 4h between the anode and cathode, exchange one-time electrode every 30min, electrolysis temperature controls at 60 DEG C。Electrolyte is the Na of 300mg/ml₂SO₄Aqueous solution。Electrolyte is 200ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 5 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is forced out。(4) solid that solid-liquid separation obtains is dispersed in the aqueous solution containing P123, adopts magnetic agitation 3h, whipping temp 25 DEG C。P123 concentration in aqueous is 0.1mol/L。Solid concentration in aqueous is 5mg/ml。Then the centrifugal 10min of rotating speed adopting 1000rpm obtains rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) by rough graphene dispersion in deionized water, magnetic agitation 60h, whipping temp 20 DEG C are adopted。The Polypropylene Bag in 0.2 μm of aperture is used to realize solid-liquid separation the suspension after stirring。Solid is stayed in bag, and liquid is extruded。Gained solid uses alkalescence (the NaOH aqueous solution of pH=11) washing, acid (the HCl/water solution of pH=4) washing and deionized water respectively to wash 6 times successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is at 30mg/ml。Then adopt Polypropylene Bag (5 μm of aperture) filter pressing, lyophilization 48h, collect Graphene sample。After testing, the productivity of Graphene is more than 84%, and phosphorus content is more than 99% (XPS detection), and in sample, the Graphene number of plies of more than 87% is 1-4 layer (comprehensive detection)。

Embodiment 4:

(1) 10.0g micro crystal graphite raw ore is adopted ultrasonic grinding。Ultrasonic frequency is 25KHz, power density 800w, time 15h, temperature 40 DEG C。After pulverizing, the mean diameter of micro crystal graphite raw ore is at 500nm。(2) electrode that the micro crystal graphite original ore powder after Ultrasonic Pulverization is pressed into membranaceous self-supporting does anode and negative electrode。The thickness of anode and negative electrode is 1mm。Anode and negative electrode all contain the graphite content of mass fraction more than 50%, and its resistivity is 0.5 kilo-ohm of momme (0.5K Ω m), has hole, and specific surface area is every gram of (4m of 4 square meter²/ g)。The pressure of electrode pressing is 5MPa, and temperature is 25 DEG C。8 anodes and 8 two kinds of electrodes of negative electrode form array。The spacing of anode and negative electrode is 10mm。Adopting polystyrene film to separate between anode and negative electrode, the average pore size of polystyrene film is 5 μm。(3) apply the alternating voltage of 6V, electrolysis 24h between the anode and cathode, convert primary current direction every 1min。Electrolysis temperature controls at 25 DEG C。Electrolyte is made up of dimethyl carbonate and sodium perchlorate, and the weight/mass percentage composition of sodium perchlorate is 15%。Electrolyte comprises the water of mass percent 1%。Electrolyte is 30ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 20 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is extruded。(4) solid that solid-liquid separation obtains is dispersed in N,N-dimethylformamide (DMF) ultrasonic。Supersonic frequency is 30KHz, and power density is 800w, time 4h, temperature 25 DEG C。Solid concentration in DMF is 0.01mg/ml。Then the centrifugal 30min of rotating speed adopting 500rpm obtains rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) by rough graphene dispersion in N,N-dimethylformamide (DMF) ultrasonic。Supersonic frequency is 10KHz, and power density is 300w, time 10min, temperature 30 DEG C。Suspension after ultrasonic is centrifuged 10min under the rotating speed of 3000rpm。The centrifugal solid obtained use alkalescence (the NaOH aqueous solution of pH=11) washing, acid (aqueous hydrochloric acid solution of pH=4) washing and deionized water respectively wash 5 times successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is at 5mg/ml。Then polystyrene film (20 μm of aperture) is adopted to filter, 70 DEG C of dry 60h, collect Graphene sample。The productivity 85% of Graphene, phosphorus content 99% (XPS detection), Graphene number of plies 1-4 layer (comprehensive detection) of 83% in sample。

Embodiment 5:

(2) make binding agent with politef (PTFE), not sufficiently delaminated raw ore is pressed into the columnar electrode of self-supporting side and does the thickness of anode and negative electrode, anode and negative electrode and be 5mm。The mass ratio of PTFE and not sufficiently delaminated raw ore is 0.05g/g。Anode and negative electrode all contain the graphite content of mass fraction more than 50%, and its resistivity is 0.3 kilo-ohm of momme (0.3K Ω m), have hole, specific surface area 4 every gram of (4m of square meter²/ g)。The pressure of electrode pressing is 45MPa, and temperature is 80 DEG C。Anode and the two kinds of electrode of negative electrode form array。The spacing of anode and negative electrode is at 1mm。Polypropylene screen interval is adopted between anode and negative electrode。The average pore size of polypropylene screen is 10 μm。(3) apply the DC voltage of+10V to-10V, electrolysis 48h between the anode and cathode, exchange one-time electrode every 1h。Electrolysis temperature controls at 40 DEG C。Electrolyte is by Al (NO₃)₃, LiCl and Ethyl methyl carbonate form。The weight/mass percentage composition of LiCl is 30%, Al (NO₃)₃Weight/mass percentage composition be 3%。Electrolyte comprises the water of mass percent 5%。Electrolyte is 50ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 1 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is thrown out of。(4) solid that solid-liquid separation obtains is dispersed in dimethyl carbonate (DMC), adopts magnetic agitation 30h, whipping temp 60 DEG C。Solid concentration in DMC is 5mg/ml。Then the centrifugal 10min of 2000rpm is adopted to obtain rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) rough Graphene is placed in acetonitrile ultrasonic。Supersonic frequency is 30KHz, and power density is 800w, time 30min, temperature 30 DEG C。Suspension after ultrasonic is centrifuged 30min under the rotating speed of 10000rpm。The centrifugal solid obtained uses alkalescence (the NaOH aqueous solution of pH=11) washing, acid (the HCl/water solution of pH=4) washing and deionized water respectively to wash 6 times successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is at 150mg/ml。Then adopt Polythene Bag (2 μm of aperture) filter pressing, lyophilization 36h, collect Graphene sample。After testing, the productivity of Graphene is more than 84%, and phosphorus content is more than 99% (XPS detection), and in sample, the Graphene number of plies of more than 87% is 1-4 layer (comprehensive detection)。

Embodiment 6:

(1) by the agate ball abrading-ball that 1500.0g diameter is 1-1.3cm, 10.0g micro crystal graphite raw ore seals in air atmosphere to agate jar, is then placed on planetary ball mill by ball grinder and with the rotating speed ball milling 2 hours of 580rpm。Being taken out by agate ball with tweezers, after ball milling, the mean diameter of micro crystal graphite raw ore is at 1 μm。(2) make binding agent with carboxymethyl cellulose (CMC), the micro crystal graphite original ore powder after ball milling is pressed into cylindrical electrode and does the diameter of anode and negative electrode, anode and negative electrode and be 3mm。The mass ratio of CMC and micro crystal graphite original ore powder is 0.25g/g。Anode and negative electrode all contain the graphite content of mass fraction more than 50%, and its resistivity is 0.3 kilo-ohm of momme (0.3K Ω m), have hole, specific surface area 4 every gram of (4m of square meter²/ g)。The pressure of electrode pressing is 20MPa, and temperature is 350 DEG C。16 anodes and 16 two kinds of electrodes of negative electrode form array。The spacing of anode and negative electrode is at 45mm。Polypropylene Bag interval is adopted between anode and negative electrode。The average pore size of Polypropylene Bag is 20 μm。(3) apply the DC voltage of+10V to-10V, electrolysis 72h between the anode and cathode, exchange one-time electrode every 1h。Electrolysis temperature controls at 40 DEG C。Electrolyte is by LiPF₆Form with Allyl carbonate。LiPF₆Mass fraction be 5%。Electrolyte is 10ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 2 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is thrown out of。(4) solid that solid-liquid separation obtains is dispersed in Allyl carbonate (PC), mechanical agitation 20h, whipping temp 30 DEG C。Solid concentration in PC is 2mg/ml。The centrifugal 30min of rotating speed adopting 500rpm obtains rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) by rough graphene dispersion in Allyl carbonate (PC) ultrasonic。Supersonic frequency is 20KHz, and power density is 500w, time 30min, temperature 25 DEG C。Suspension after ultrasonic adopts the centrifugal 30min of rotating speed of 5000rpm。The centrifugal solid obtained uses alkalescence (the NaOH aqueous solution of 0.01mol/L) washing, acid (the HCl/water solution of 0.005mol/L) washing and deionized water to wash 6 times respectively successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is for 50mg/ml。Then at 80 DEG C of dry 10h, Graphene sample is collected。The productivity 85% of Graphene, phosphorus content more than 99% (XPS detection), Graphene number of plies 1-3 atomic layer (comprehensive detection) of 87% in sample。

Embodiment 7:

(2) making binding agent with politef (PTFE), platinized platinum is supporter, not sufficiently delaminated raw ore is compressed on the square columnar electrode made with supporter platinized platinum side and does anode and negative electrode。The compacting thickness of not sufficiently delaminated raw ore is 4mm。The mass ratio of PTFE and not sufficiently delaminated raw ore is 0.15g/g。Anode and negative electrode all contain the graphite content of mass fraction more than 50%, and its resistivity is 0.3 kilo-ohm of momme (0.3K Ω m), have hole, specific surface area 4 every gram of (4m of square meter²/ g)。The pressure of electrode pressing is 15MPa, and temperature is 150 DEG C。Anode and the two kinds of electrode of negative electrode form array。The spacing of anode and negative electrode is at 2mm。(3) apply the DC voltage of+10V to-10V, electrolysis 72h between the anode and cathode, exchange one-time electrode every 1h。Electrolysis temperature controls at 40 DEG C。Electrolyte is by KClO₄, NaNO₃Form with dimethyl carbonate。KClO₄Weight/mass percentage composition be 10%, NaNO₃Weight/mass percentage composition be 1%。Electrolyte comprises the water of mass percent 10%。Electrolyte is 60ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 0.45 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is thrown out of。(4) solid that solid-liquid separation obtains is dispersed in oxolane (THF) ultrasonic。Supersonic frequency is 30KHz, and power density is 1000w, time 30min, temperature 25 DEG C。Solid concentration in THF is 5mg/ml。Then the centrifugal 20min of rotating speed adopting 1000rpm obtains rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) rough Graphene is placed in dimethyl carbonate (DMC) ultrasonic。Supersonic frequency is 25KHz, and power density is 1000w, time 15min, temperature 25 DEG C。Suspension after ultrasonic is centrifugal 10min under 5000rpm。The centrifugal solid obtained uses alkalescence (NaOH of 0.1mol/L) solution washing, acidity (the HCl/water solution of 0.05mol/L) aqueous solution respectively to wash 3 times and deionized water wash 6 times successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is for 300mg/ml。Then porous polypropylene film (average pore size of film 0.22 μm) is used to filter, the dry 96h when 80 DEG C, then collects detection Graphene sample。The productivity 85% of Graphene, phosphorus content 99% (XPS detection), Graphene number of plies 1-4 layer (comprehensive detection) of 80% in sample。

Embodiment 8:

(1) pulverizer is adopted to pulverize in 10.0g micro crystal graphite raw ore。After pulverizing, the mean diameter of micro crystal graphite raw ore is 2 μm。(2) with polyvinyl alcohol (PVA) for binding agent, graphite paper thick for 5mm is supporter, the micro crystal graphite original ore powder after Ultrasonic Pulverization is compressed on graphite paper both sides and does film-like electrode and do anode and negative electrode。The mass ratio that the thickness of micro crystal graphite original ore powder is 1mm, PVA and not sufficiently delaminated raw ore is 0.10g/g。Anode and negative electrode all contain the graphite content of mass fraction more than 50%, and its resistivity is 0.5 kilo-ohm of momme (0.5K Ω m), has hole, and specific surface area is every gram of (4m of 4 square meter²/ g)。The pressure of electrode pressing is 50MPa, and temperature is 25 DEG C。8 anodes and 8 two kinds of electrodes of negative electrode form array。The spacing of anode and negative electrode is 5mm。Adopting polystyrene film to separate between anode and negative electrode, the average pore size of polystyrene film is 2 μm。(3) apply the DC voltage of+10V to-10V, electrolysis 12h between the anode and cathode, exchange one-time electrode every 1h。Electrolysis temperature controls at 60 DEG C。Electrolyte is 1,3-methylimidazole perchlorate, comprises the water of mass percent 20% in electrolyte。Electrolyte is 10ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 0.2 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is thrown out of。(4) solid that solid-liquid separation obtains is dispersed in the aqueous solution containing F127, adopts mechanical agitation 10h, whipping temp 60 DEG C。F127 concentration in aqueous is 0.01mol/L。Solid concentration in aqueous is 10mg/ml。Then the centrifugal 20min of rotating speed adopting 1500rpm obtains rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) by rough graphene dispersion in deionized water, magnetic agitation 60h, whipping temp 20 DEG C are adopted。The Polypropylene Bag in 0.2 μm of aperture is used to realize solid-liquid separation the suspension after stirring。Solid is stayed in bag, and liquid is extruded。Gained solid uses alkalescence (the NaOH aqueous solution of pH=11) washing, acid (the HCl/water solution of pH=4) washing and deionized water respectively to wash 6 times successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is at 30mg/ml。Then adopt Polypropylene Bag (5 μm of aperture) filter pressing, lyophilization 48h, collect Graphene sample。After testing, the productivity of Graphene is more than 84%, and phosphorus content is more than 99% (XPS detection), and in sample, the Graphene number of plies of more than 87% is 1-4 layer (comprehensive detection)。

Embodiment 9:

(1) by zirconia ball abrading-ball that 1500.0g diameter is 3-8mm; 10.0g micro crystal graphite raw ore and 60ml dispersant protect lower seal in zirconia ball grinding jar at nitrogen atmosphere, then ball grinder is placed on planetary ball mill and with the rotating speed ball milling 30 hours of 300 revs/min。With tweezers, zirconia ball is taken out。Dispersant is made up of Allyl carbonate and sodium perchlorate, and the mass percent of sodium perchlorate is 5%。The ratio of dispersant and micro crystal graphite raw ore is 6ml/g。After ball milling, the mean diameter of micro crystal graphite raw ore is at 2 μm。(2) the micro crystal graphite original ore powder after ball milling is directly loadable in Polythene Bag, makes anode and negative electrode。Distance between anode and negative electrode is 5mm, and the average pore size of Polythene Bag is 0.2 μm。(3) apply the DC voltage of+10V to-10V, electrolysis 72h between the anode and cathode, exchange one-time electrode every 1h。Electrolysis temperature controls at 40 DEG C。Electrolyte is by KClO₄, NaNO₃Form with dimethyl carbonate。KClO₄Weight/mass percentage composition be 10%, NaNO₃Weight/mass percentage composition be 1%。Electrolyte comprises the water of mass percent 10%。Electrolyte is 60ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 0.45 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is thrown out of。(4) solid dispersion solid-liquid separation obtained is ultrasonic in acetone。Supersonic frequency is 10KHz, power density 500w, time 1h, temperature 25 DEG C。Solid concentration in acetone is 10mg/ml。Then the centrifugal 20min of rotating speed adopting 1000rpm obtains rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) by rough graphene dispersion in 2-methyl pyrrolidone ultrasonic。Supersonic frequency is 30KHz, and power density is 800w, time 5h, temperature 30 DEG C。Suspension after ultrasonic adopts the centrifugal 10min of rotating speed of 4000rpm。The centrifugal solid obtained uses alkalescence (the NaOH aqueous solution of 0.1mol/L) washing, acid (the HCl/water solution of 0.05mol/L) washing and each 6 times of deionized water wash successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is for 80mg/ml。Then use porous polypropylene bag (average pore size of bag 15 μm) filter pressing, lyophilization 24h, collect and detect gained Graphene sample。The product of Graphene 250 grams, phosphorus content 99% (XPS detection), in sample, the Graphene of more than 88% is 1-4 atomic layer (comprehensive detection)。

Embodiment 10:

(1) by zirconia ball abrading-ball that 1500.0g diameter is 3-8mm; 10.0g micro crystal graphite raw ore and 60ml dispersant seal under nitrogen protection to zirconia ball grinding jar, then ball grinder is placed on planetary ball mill and with the rotating speed ball milling 30 hours of 300 revs/min。With tweezers, zirconia ball is taken out, milled sample is directly installed in negative electrode and the anode of making electrolyzer in two Polythene Bags。Dispersant is by dimethyl carbonate and LiPF₆Composition, LiPF₆Mass percent be 2%。The ratio of dispersant and micro crystal graphite raw ore is 6ml/g。After ball milling, the mean diameter of micro crystal graphite raw ore is at 2 μm。(2) the micro crystal graphite original ore powder after ball milling is directly loadable in Polythene Bag, makes anode and negative electrode。Distance between anode and negative electrode is 5mm, and the average pore size of Polythene Bag is 0.2 μm。(3) apply the DC voltage of+10V to-10V, electrolysis 72h between the anode and cathode, exchange one-time electrode every 1h。Electrolysis temperature controls at 40 DEG C。Electrolyte is by LiPF₆Form with Allyl carbonate。LiPF₆Mass fraction be 5%。Electrolyte is 10ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 2 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is thrown out of。(4) solid that solid-liquid separation obtains is dispersed in dimethyl carbonate (DMC), adopts magnetic agitation 30h, whipping temp 60 DEG C。Solid concentration in DMC is 5mg/ml。Then the centrifugal 10min of rotating speed adopting 2000rpm obtains rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) by rough graphene dispersion in Allyl carbonate ultrasonic。Supersonic frequency is 20KHz, and power density is 500w, time 30min, temperature 25 DEG C。Suspension after ultrasonic adopts the centrifugal 30min of rotating speed of 5000rpm。The centrifugal solid obtained uses alkalescence (the NaOH aqueous solution of 0.01mol/L) washing, acid (the HCl/water solution of 0.005mol/L) washing and deionized water to wash 6 times respectively successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is for 50mg/ml。Then at 80 DEG C of dry 10h, Graphene sample is collected。The productivity 85% of Graphene, phosphorus content more than 99% (XPS detection), Graphene number of plies 1-3 atomic layer (comprehensive detection) of 87% in sample。

Embodiment 11:

(1) by zirconia ball abrading-ball that 1500.0g diameter is 3-8mm; 10.0g micro crystal graphite raw ore and 60ml dispersant seal under nitrogen protection to zirconia ball grinding jar, then ball grinder is placed on planetary ball mill and with the rotating speed ball milling 30 hours of 300 revs/min。With tweezers, zirconia ball is taken out。Dispersant is made up of DMF and LiCl, and the mass percent of LiCl is 5%。The ratio of dispersant and micro crystal graphite raw ore is 6ml/g。After ball milling, the mean diameter of micro crystal graphite raw ore is at 2 μm。(2) the micro crystal graphite original ore powder after ball milling is directly loadable in Polythene Bag, makes anode and negative electrode。Distance between anode and negative electrode is 5mm, and the average pore size of Polythene Bag is 0.2 μm。(3) apply the DC voltage of+10V to-10V, electrolysis 48h between the anode and cathode, exchange one-time electrode every 1h。Electrolysis temperature controls at 40 DEG C。Electrolyte is by Al (NO₃)₃, LiCl and Ethyl methyl carbonate form。The weight/mass percentage composition of LiCl is 30%, Al (NO₃)₃Weight/mass percentage composition be 3%。Electrolyte comprises the water of mass percent 5%。Electrolyte is 50ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 1 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is thrown out of。(4) solid that solid-liquid separation obtains is dispersed in acetonitrile, adopts magnetic agitation 60h, whipping temp 30 DEG C。Solid concentration in acetonitrile is 20mg/ml。Then adopt the centrifugal 15min of rotating speed of 1500rpm, obtain rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) by rough graphene dispersion in N-Methyl pyrrolidone, magnetic agitation 3h, whipping temp 60 DEG C are adopted。Suspension after stirring is adopted the centrifugal 30min of rotating speed of 3000rpm。The centrifugal solid obtained uses alkalescence (the NaOH aqueous solution of 0.01mol/L) washing, acid (the HCl/water solution of 0.005mol/L) washing and deionized water to wash 6 times respectively successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is for 100mg/ml。Then adopt Polythene Bag filter pressing, 80 DEG C of dry 40h, collect Graphene sample。The productivity 81% of Graphene, phosphorus content more than 99% (XPS detection), Graphene number of plies 1-4 atomic layer (comprehensive detection) of 85% in sample。

Embodiment 12:

(1) by alumina balls abrading-ball that 500.0g diameter is 8-15mm; 10.0g micro crystal graphite raw ore and 300ml dispersant are in air conservation lower seal to agate jar, then ball grinder is placed on planetary ball mill and with the rotating speed ball milling 60 hours of 100 revs/min。With tweezers, alumina balls are taken out。Dispersant is the NaOH aqueous solution of mass fraction 20%。The ratio of dispersant and micro crystal graphite raw ore raw material is 30ml/g。After ball milling, the mean diameter of micro crystal graphite raw ore is at 5 μm。(2) the micro crystal graphite original ore powder after ball milling is directly loadable in Polythene Bag, makes anode and negative electrode。Distance between anode and negative electrode is 5mm, and the average pore size of Polythene Bag is 0.2 μm。(3) applying the DC voltage of+10V to-10V, electrolysis 4h between the anode and cathode, exchange one-time electrode every 30min, electrolysis temperature controls at 60 DEG C。Electrolyte is the Na of 300mg/ml₂SO₄Aqueous solution。Electrolyte is 200ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 5 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is thrown out of。(4) solid dispersion solid-liquid separation obtained is ultrasonic in the aqueous solution containing F68。Supersonic frequency is 15KHz, and power density is 500w, time 5h, temperature 20 DEG C。F68 concentration in aqueous is 0.5mol/L。Solid concentration in aqueous is 17mg/ml。Then the centrifugal 10min of rotating speed adopting 2000rpm obtains rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) by rough graphene dispersion in deionized water, adopt mechanical agitation 30h, whipping temp 40 DEG C, then use the Polythene Bag in 10 μm of aperture to realize solid-liquid separation。Solid is stayed in bag, and liquid is extruded。Gained solid uses alkalescence (the NaOH aqueous solution of pH=11) washing, acid (the HCl/water solution of pH=4) washing and deionized water respectively to wash 6 times successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is at 50mg/L。Then adopt polyethylene film (1 μm of aperture) sucking filtration, lyophilization 10h, collect Graphene sample。After testing, the productivity of Graphene is more than 84%, and phosphorus content is more than 99% (XPS detection), and in sample, the Graphene number of plies of more than 87% is 1-4 layer (comprehensive detection)。

Embodiment 13:

(1) by alumina balls abrading-ball that 500.0g diameter is 8-15mm; 10.0g micro crystal graphite raw ore and 300ml dispersant are in air conservation lower seal to agate jar, then ball grinder is placed on planetary ball mill and with the rotating speed ball milling 60 hours of 100 revs/min。With tweezers, alumina balls are taken out。Dispersant is the KOH aqueous solution of mass fraction 2%。The ratio of dispersant and micro crystal graphite raw ore raw material is 30ml/g。After ball milling, the mean diameter of micro crystal graphite raw ore is at 5 μm。(2) the micro crystal graphite original ore powder after ball milling is directly loadable in Polythene Bag, makes anode and negative electrode。Distance between anode and negative electrode is 5mm, and the average pore size of Polythene Bag is 0.2 μm。(3) applying the DC voltage of+8V to-8V, electrolysis 60h between the anode and cathode, exchange one-time electrode every 3h, electrolysis temperature controls at 40 DEG C。Electrolyte is the H of 100mg/ml₂SO₄Aqueous solution。Electrolyte is 100ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 0.2 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is thrown out of。(4) solid that solid-liquid separation obtains is dispersed in deionized water for ultrasonic。Supersonic frequency is 10KHz, and power density is 300w, time 3h, temperature 40 DEG C。Solid concentration in deionized water is 5mg/ml。Then the centrifugal 5min of rotating speed adopting 3000rpm obtains rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) rough Graphene is put in deionized water, adopt magnetic agitation 15h, whipping temp 20 DEG C, then use the polystyrene film in 20 μm of aperture to realize solid-liquid separation。Gained solid uses alkalescence (the NaOH aqueous solution of pH=11) washing, acid washing (aqueous hydrochloric acid solution of pH=5) and deionized water to wash 5 times respectively successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is at 100mg/ml。Then with (average pore size of bag 0.2 μm) filter pressing in porous polypropylene bag, when 80 DEG C, dry 48h Graphene, collects Graphene sample。The productivity 83% of Graphene, phosphorus content 99% (XPS detection), in sample, the Graphene number of plies of more than 86% is 1-4 layer (comprehensive detection)。

Embodiment 14:

(1) by alumina balls abrading-ball that 500.0g diameter is 8-15mm; 10.0g micro crystal graphite raw ore and 300ml dispersant are in air conservation lower seal to agate jar, then ball grinder is placed on planetary ball mill and with the rotating speed ball milling 60 hours of 100 revs/min。With tweezers, alumina balls are taken out。Dispersant is the NH of mass fraction 10%₃·H₂O aqueous solution。The ratio of dispersant and micro crystal graphite raw ore raw material is 30ml/g。After ball milling, the mean diameter of micro crystal graphite raw ore is at 5 μm。(2) the micro crystal graphite original ore powder after ball milling is directly loadable in Polythene Bag, makes anode and negative electrode。Distance between anode and negative electrode is 5mm, and the average pore size of Polythene Bag is 0.2 μm。(3) applying the DC voltage of+8V to-8V, electrolysis 60h between the anode and cathode, exchange one-time electrode every 3h, electrolysis temperature controls at 40 DEG C。Electrolyte is the H of 100mg/ml₂SO₄Aqueous solution。Electrolyte is 100ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 0.2 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is thrown out of。(4) solid that solid-liquid separation obtains is dispersed in deionized water for ultrasonic。Supersonic frequency is 5KHz, and power density is 100w, time 10h, temperature 25 DEG C。Solid concentration in deionized water is 0.1mg/ml, then adopts the centrifugal 30min of rotating speed of 1000rpm to obtain rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) rough graphene dispersion is ultrasonic in deionized water。Supersonic frequency is 15KHz, and power density is 500w, time 20min, temperature 20 DEG C。Suspension after ultrasonic adopts the centrifugal 20min of rotating speed of 5000rpm。The centrifugal solid obtained uses alkalescence (the NaOH aqueous solution of 0.01mol/L) washing, acid (the HCl/water solution of 0.005mol/L) washing and deionized water to wash 6 times respectively successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is for 20mg/ml。Then adopt polyethylene film (1 μm of aperture) sucking filtration, 120 DEG C of dry 10h, collect Graphene sample。The productivity 81% of Graphene, phosphorus content more than 99% (XPS detection), Graphene number of plies 1-4 atomic layer (comprehensive detection) of 90% in sample。

Embodiment 15:

(1) 20.0g micro crystal graphite raw ore is adopted ultrasonic grinding together with 60ml dispersant。Ultrasonic frequency is 20KHz, power density 500w, time 28h, temperature 25 DEG C。Dispersant is the aluminum nitrate aqueous solution of mass fraction 8%。The ratio of dispersant and micro crystal graphite raw ore raw material is 3ml/g。After pulverizing, the mean diameter of micro crystal graphite raw ore is 3mm。(2) electrode that the micro crystal graphite original ore powder after Ultrasonic Pulverization is pressed into membranaceous self-supporting does anode and negative electrode, the thickness of anode and negative electrode is 1mm, anode and negative electrode all contain the graphite content of mass fraction more than 50%, its resistivity is 0.5 kilo-ohm of momme (0.5K Ω m), having hole, specific surface area is every gram of (4m of 4 square meter²/ g)。The pressure of electrode pressing is 5MPa, and temperature is 25 DEG C。8 anodes and 8 two kinds of electrodes of negative electrode form array。The spacing of anode and negative electrode is 10mm。Adopting polystyrene film to separate between anode and negative electrode, the average pore size of polystyrene film is 5 μm。(3) apply the DC voltage of+9V to-9V, electrolysis 12h between the anode and cathode, exchange one-time electrode every 1h。Electrolysis temperature controls at 60 DEG C。Electrolyte is N-ethylpyridine tetrafluoroborate。Electrolyte comprises the water of mass percent 10%。Electrolyte is 50ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 0.2 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is thrown out of。(4) solid that solid-liquid separation obtains is dispersed in deionized water for ultrasonic。Supersonic frequency is 10KHz, and power density is 300w, time 3h, temperature 40 DEG C。Solid concentration in deionized water is 5mg/ml。Then the centrifugal 5min of rotating speed adopting 3000rpm obtains rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) by rough graphene dispersion in deionized water, magnetic agitation 60h, whipping temp 30 DEG C are adopted。Suspension after stirring is adopted the centrifugal 20min of rotating speed of 2800rpm。The centrifugal solid obtained uses alkalescence (the NaOH aqueous solution of 0.01mol/L) washing, acid (the HCl/water solution of 0.005mol/L) washing and deionized water to wash 6 times respectively successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is for 300mg/ml。Then adopt Polythene Bag (1 μm of aperture) filter pressing, 80 DEG C of dry 30h, collect Graphene sample。The productivity 81% of Graphene, phosphorus content more than 99% (XPS detection), Graphene number of plies 1-4 atomic layer (comprehensive detection) of 87% in sample。

Embodiment 16:

(1) 1.0g micro crystal graphite raw ore is adopted ultrasonic grinding together with 80ml dispersant。Ultrasonic frequency is 25KHz, power density 800w, time 15h, temperature 40 DEG C。Dispersant is the lithium perchlorate aqueous solution of mass fraction 1.5%。The ratio of dispersant and micro crystal graphite raw ore raw material is 80ml/g。After pulverizing, the mean diameter of micro crystal graphite raw ore is at 500nm。(2) with polyvinyl alcohol (PVA) for binding agent, graphite paper thick for 5mm is supporter, the micro crystal graphite original ore powder after Ultrasonic Pulverization is compressed on graphite paper both sides and does film-like electrode and do anode and negative electrode。The mass ratio that the thickness of micro crystal graphite original ore powder is 1mm, PVA and micro crystal graphite original ore powder is 0.10g/g。Anode and negative electrode all contain the graphite content of mass fraction more than 50%, and its resistivity is 0.5 kilo-ohm of momme (0.5K Ω m), has hole, and specific surface area is every gram of (4m of 4 square meter²/ g)。The pressure of electrode pressing is 50MPa, and temperature is 25 DEG C。8 anodes and 8 two kinds of electrodes of negative electrode form array。The spacing of anode and negative electrode is 5mm。Adopting polystyrene film to separate between anode and negative electrode, the average pore size of polystyrene film is 2 μm。(3) apply the alternating voltage of 10V, electrolysis 30h between the anode and cathode, convert primary current direction every 30min。Electrolysis temperature controls at 60 DEG C。Electrolyte is 1-normal-butyl-1-crassitude two (trimethyl fluoride sulfonyl) acid imide。Electrolyte comprises the water of mass percent 1%。Electrolyte is 20ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 0.2 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is thrown out of。(4) solid that solid-liquid separation obtains is dispersed in deionized water for ultrasonic。Supersonic frequency is 5KHz, and power density is 100w, time 10h, temperature 25 DEG C。Solid concentration in deionized water is 0.1mg/ml, then adopts the centrifugal 30min of rotating speed of 1000rpm to obtain rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) rough Graphene is put in deionized water, adopt magnetic agitation 15h, whipping temp 20 DEG C, then use the polystyrene film in 20 μm of aperture to realize solid-liquid separation。Gained solid uses alkalescence (the NaOH aqueous solution of pH=11) washing, acid washing (aqueous hydrochloric acid solution of pH=5) and deionized water to wash 5 times respectively successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is at 100mg/ml。Then with (average pore size of bag 0.2 μm) filter pressing in porous polypropylene bag, when 80 DEG C, dry 48h Graphene, collects Graphene sample。The productivity 83% of Graphene, phosphorus content 99% (XPS detection), in sample, the Graphene number of plies of more than 86% is 1-4 layer (comprehensive detection)。Embodiment 17:

(1) 5.0g micro crystal graphite raw ore is adopted ultrasonic grinding together with 150ml dispersant。Ultrasonic frequency is 30KHz, power density 1000w, time 2h, temperature 60 C。Dispersant is the aqueous sodium persulfate solution of mass fraction 15%。The ratio of dispersant and micro crystal graphite raw ore raw material is 30ml/g。After pulverizing, micro crystal graphite raw ore mean diameter is at 20 μm。(2) electrode that the micro crystal graphite original ore powder after Ultrasonic Pulverization is pressed into membranaceous self-supporting does anode and negative electrode, the thickness of anode and negative electrode is 1mm, anode and negative electrode all contain the graphite content of mass fraction more than 50%, its resistivity is 0.5 kilo-ohm of momme (0.5K Ω m), having hole, specific surface area is every gram of (4m of 4 square meter²/ g)。The pressure of electrode pressing is 5MPa, and temperature is 25 DEG C。8 anodes and 8 two kinds of electrodes of negative electrode form array。The spacing of anode and negative electrode is 10mm。Adopting polystyrene film to separate between anode and negative electrode, the average pore size of polystyrene film is 5 μm。(3) applying the DC voltage of+10V to-10V, electrolysis 4h between the anode and cathode, exchange one-time electrode every 30min, it is 60 DEG C that electrolysis temperature controls。Electrolyte is the Na of 300mg/ml₂SO₄Aqueous solution。Electrolyte is 200ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 5 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is thrown out of。(4) solid that solid-liquid separation obtains is dispersed in deionized water for ultrasonic。Supersonic frequency is 10KHz, and power density is 300w, time 3h, temperature 40 DEG C。Solid concentration in deionized water is 5mg/ml。Then the centrifugal 5min of rotating speed adopting 3000rpm obtains rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) by rough graphene dispersion in deionized water, adopt mechanical agitation 30h, whipping temp 40 DEG C, then use the Polythene Bag in 10 μm of aperture to realize solid-liquid separation。Solid is stayed in bag, and liquid is extruded。Gained solid uses alkalescence (the NaOH aqueous solution of pH=11) washing, acid (the HCl/water solution of pH=4) washing and deionized water respectively to wash 6 times successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is at 50mg/ml。Then adopt polyethylene film (1 μm of aperture) sucking filtration, lyophilization 10h, collect Graphene sample。After testing, the productivity of Graphene is more than 84%, and phosphorus content is more than 99% (XPS detection), and in sample, the Graphene number of plies of more than 87% is 1-4 layer (comprehensive detection)。

Embodiment 18:

(2) make binding agent with politef (PTFE), not sufficiently delaminated raw ore is pressed into the columnar electrode of self-supporting side and does the thickness of anode and negative electrode, anode and negative electrode and be 5mm。The mass ratio of PTFE and not sufficiently delaminated raw ore is 0.05g/g。Anode and negative electrode all contain the graphite content of mass fraction more than 50%, and its resistivity is 0.3 kilo-ohm of momme (0.3K Ω m), have hole, specific surface area 4 every gram of (4m of square meter²/ g)。The pressure of electrode pressing is 45MPa, and temperature is 80 DEG C。Anode and the two kinds of electrode of negative electrode form array。The spacing of anode and negative electrode is at 1mm。Polypropylene screen interval is adopted between anode and negative electrode。The average pore size of polypropylene screen is 10 μm。(3) apply the DC voltage of+10V to-10V, electrolysis 72h between the anode and cathode, exchange one-time electrode every 1h。Electrolysis temperature controls at 40 DEG C。Electrolyte is by LiPF₆Form with Allyl carbonate。LiPF₆Mass fraction be 5%。Electrolyte is 10ml/g with the ratio of graphite content gross mass in electrode。After electrolysis terminates, use the Polythene Bag in 2 μm of aperture to realize solid and separate with electrolyte。Solid is stayed in bag, and electrolyte is thrown out of。(4) solid that solid-liquid separation obtains is dispersed in Ethyl methyl carbonate, adopts magnetic agitation 15h, whipping temp 40 DEG C。Solid concentration in Ethyl methyl carbonate is 5mg/ml。The centrifugal 10min of rotating speed adopting 1500rpm obtains rough Graphene and not sufficiently delaminated raw ore。The centrifugal liquid obtained and not sufficiently delaminated raw ore are recycled。(5) by rough graphene dispersion in acetamide, adopt mechanical agitation 30h, whipping temp 60 DEG C, then adopt the centrifugal 30min of rotating speed of 2000rpm。The centrifugal solid obtained uses alkalescence (the NaOH aqueous solution of 0.01mol/L) washing, acid (the HCl/water solution of 0.005mol/L) washing and deionized water to wash 6 times respectively successively。In washing, the concentration of Graphene (with carbon Mass Calculation) is for 200mg/ml。Then adopt polystyrene bag (10 μm of aperture) filter pressing, 120 DEG C of dry 10h, collect Graphene sample。The productivity 81% of Graphene, phosphorus content more than 99% (XPS detection), Graphene number of plies 1-3 atomic layer (comprehensive detection) of 85% in sample。

Claims

1. the method being prepared Graphene by graphite raw ore electrolysis, it is characterised in that comprise the following steps:

(1) by micro crystal graphite crushing raw ore, sieving, fully not broken raw materials recovery utilizes；

(2) micro crystal graphite original ore powder or not sufficiently delaminated raw ore are made electrode；

(3) electrolysis in electrolyzer of made electrode, solid-liquid separation；

(4) separate the solid obtained to peel off further, obtain not sufficiently delaminated raw ore, rough Graphene；

(5) rough Graphene separating-purifying goes out Graphene；

The broken Mechanical Crushing that comprises of described step (1) micro crystal graphite raw ore, ultrasonic grinding method；After broken, the particle diameter of micro crystal graphite raw ore is at 10 nanometers to 5 millimeters；Shattering process adds dispersant, or is not added with dispersant；

Micro crystal graphite original ore powder or not sufficiently delaminated raw ore are made electrode and are included micro crystal graphite breeze or not sufficiently delaminated raw ore to suppress to form shaped electrode by described step (2), are maybe directly placed in polymer pouches using the micro crystal graphite original ore powder after broken or not sufficiently delaminated raw ore and use as electrode；

Described step (3) electrolyzer includes the electrod-array of multiple electrode composition, and multiple electrolyzers form cell array again, and each electrolyzer is independent is powered by single power supply, or is together in parallel and is powered by single power supply；

Anode electrode in described step (3) electrolyzer and the spacing of cathode electrode between 1 millimeter to 50 millimeter, use between anode electrode and cathode electrode include porous insulation polymer pouches or intermembranous every；

Described step (3) applies direct current or the alternating voltage of 4 volts to 10 volts between anode and negative electrode；Each electrolysis time is between 2 hours to 144 hours, and the time of conversion charging current or voltage direction, electrolysis temperature was between 20 degrees Celsius to 60 degrees Celsius between 10 seconds to 12 hours；Electrolyte adopts aqueous electrolyte or non-aqueous electrolyte；The ratio of electrolyte and electrode controls between 1 ml/g to 100 ml/g；

In described step (3), the solid-liquid separation of electrolysis rear electrode and electrolyte uses and includes average pore size porous polymer bag between 0.2 micron to 20 micron or film, and solid is stayed in bag, and liquid is thrown out of, extrudes, extrudes or flows out；

The peeling off further of described step (4) electrode include utilizing ultrasonic or stirring to make electrolysis after electrode peel off further；Adopt centrifugal method to realize solid-liquid separation, obtain not sufficiently delaminated raw ore and rough Graphene；If using aqueous electrolyte, hydrophilic glyoxaline ion liquid electrolyte, hydrophilic pyridine ionic liquid electrolyte or hydrophilic pyrrole ionic liquid electrolyte electrolysis electrode, then peeling off the solvent used further is water or the aqueous solution containing surfactant, and solid concentration in water or the aqueous solution containing surfactant is between 0.01 mg/ml to 20 mg/ml；If using the electrolyte electrolysis electrode containing cyclic carbonate or linear carbonate, then peeling off the solvent used further is organic solvent, and solid concentration in organic solvent is between 0.01 mg/ml to 20 mg/ml；

The separating-purifying of described step (5) Graphene comprises four steps: (1) by rough graphene dispersion in a solvent, adopts ultrasonic or stirring to realize separating of Graphene and solid impurity；(2) solid alkaline aqueous solution washing step (1) prepared removes surface solid phase impurity；(3) the acidic aqueous solution washing of the solid product after alkali cleaning is neutralized, and utilize hydrion to replace other non-carbon ion of remnants further；(4) by the solid matter with deionized water after alkali cleaning, pickling or pure water, then adopting centrifugal, sucking filtration or filter-pressing method to realize solid-liquid separation, gained solid is further dried and obtains graphene powder。

2. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterised in that described Mechanical Crushing comprises ball milling。

3. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 2, it is characterised in that the ball milling ball of described ball milling is stainless steel ball, agate ball, zirconia ball, alumina balls or carborundum ball one therein；The diameter of ball is 3 millimeters to 15 millimeters；The material of ball grinder is rustless steel, Achates or zirconium oxide。

4. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 2, it is characterised in that the ball material mass ratio of described ball milling is 15-150:1；Rotational speed of ball-mill is: 50 revs/min to 580 revs/min；Gas is more than one in air, nitrogen, argon or helium；Ball-milling Time is 0.5 hour to 72 hours。

5. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterized in that frequency 20 KHz ultrasonic during described ultrasonic grinding is to 30 KHz, power is 500 watts to 1000 watts, 10 minutes to 30 hours time, temperature 20 degrees Celsius to 60 degrees Celsius。

6. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterized in that described dispersant comprises organic solvent, mineral acid, soluble inorganic aqueous alkali, the organic solution of soluble inorganic salt or aqueous solution, the ratio of dispersant and micro crystal graphite raw ore controls between 1 ml/g to 100 ml/g。

7. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 6, it is characterized in that described organic solvent comprises N-Methyl pyrrolidone, N, dinethylformamide, N, N-dimethyl acetylamide, N-METHYLFORMAMIDE, dimethyl sulfoxide, benzene,toluene,xylene, the one in chloroform, dichloromethane, ethanol, isopropanol, acetone, acetonitrile, cyclic carbonate or linear carbonate。

8. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 7, it is characterised in that described cyclic carbonate is Allyl carbonate, and linear carbonate is ethylene carbonate, dimethyl carbonate, diethyl carbonate or Ethyl methyl carbonate。

9. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 6, it is characterised in that described mineral acid comprises H₂SO₄、H₃PO₄、HNO₃、HClO₄、HClO₃One in S。

10. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 6, it is characterised in that described mineral acid mass concentration is between 1% to 98%。

11. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 6, it is characterised in that described soluble inorganic alkali comprises NaOH, KOH, NH₃·H₂O、Na₂CO₃、K₂CO₃In one。

12. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 6, it is characterised in that described soluble inorganic aqueous alkali mass concentration is between 0.5% to 20%。

13. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 6, it is characterised in that described soluble inorganic salt comprises perchlorate, sulfate, nitrate, phosphate, LiPF₆、LiAsF₆、LiBF₄, one in LiCl。

14. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 6, it is characterised in that described soluble inorganic saline solution mass concentration is between 0.01% to 15%。

15. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 6, it is characterised in that the mass concentration of described soluble inorganic salt organic solution is between 0.01% to 10%。

16. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, pressure used when it is characterized in that described micro crystal graphite original ore powder or not sufficiently delaminated raw ore compacting formation shaped electrode is 1-50 MPa, further, press temperature is 0 degree Celsius to 400 degrees Celsius；And compressing electrode package is containing membranaceous, circle or side column；Add binding agent during electrode pressing, or be added without binding agent。

17. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 16, it is characterised in that described compressing electrode is self-supporting or adds supporter。

18. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 17, it is characterized in that the supporter of described employing comprises platinum, gold, silver, copper, copper alloy, titanium, titanium alloy, graphite, Lead oxide brown one therein, at supporter while compacting on micro crystal graphite original ore powder or not sufficiently delaminated raw ore, or suppress micro crystal graphite original ore powder or not sufficiently delaminated raw ore on both sides simultaneously, on supporter, the micro crystal graphite original ore powder of compacting or the thickness of not sufficiently delaminated raw ore are 1 millimeter to 5 millimeters。

19. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 17, it is characterized in that the thickness of the membranaceous or square columnar electrode of described compressing self-supporting is 1 millimeter to 5 millimeters, the diameter of the columnar electrode of self-supporting circle is 1 millimeter to 5 millimeters。

20. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 16, it is characterised in that described binding agent comprises the one in polyvinyl alcohol, polyoxyethylene ether, politef, sodium carboxymethyl cellulose, carboxymethyl cellulose, Kynoar, polyurethane, Colophonium。

21. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 16, it is characterised in that the mass ratio of described binding agent and micro crystal graphite original ore powder or not sufficiently delaminated raw ore controls between 0.01 to 0.25。

22. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterised in that described electrode contains the graphite content of mass fraction more than 50%, and its resistivity is less than 1 kilo-ohm of momme, and specific surface area is more than 2 square meter every gram。

23. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterised in that described porous polymer bag or film are that polypropylene material is made, and its average pore size is between 0.2 micron to 20 micron。

24. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterised in that described aqueous electrolyte comprises HCl, HNO₃、H₂SO₄、HClO₄、HClO₃S, NaOH aqueous solution, KOH aqueous solution, Na2CO₃Aqueous solution, K₂CO₃Aqueous solution, soluble sulphate aqueous solution, soluble nitrate aqueous solution, soluble phosphoric acid saline solution, solubility perchlorate aqueous solution；In aqueous solution, the concentration of solute is between 0.01 mg/ml to 300 mg/ml。

25. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterised in that the electrolyte of described non-water system comprises the one in the mixed electrolytic solution of hydrophilic glyoxaline ion liquid, hydrophilic pyridine ionic liquid, hydrophilic pyrrole ionic liquid, cyclic carbonate electrolyte, linear carbonate electrolyte, cyclic carbonate and linear carbonate composition。

26. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 25, it is characterized in that described hydrophilic glyoxaline ion liquid, hydrophilic pyridine ionic liquid, hydrophilic pyrrole ionic liquid comprise pure glyoxaline ion liquid, pure pyridine class ionic liquid, pure pyrrole ionic liquid, one in the mixture of glyoxaline ion liquid, pyridine ionic liquid or pyrrole ionic liquid and water composition, the weight/mass percentage composition of water is between 0.001% to 20%。

27. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 25, it is characterised in that described hydrophilic glyoxaline ion liquid comprises iodate 1,3-methylimidazole, 1,3-methylimidazole Methylsulfate salt, 1,3-methylimidazole dimethyl phosphate salt, 1,3-methylimidazole tetrafluoroborate, 1,3-methylimidazole fluoroform sulphonate, 1,3-methylimidazole perchlorate, 1,3-methylimidazole nitrate, 1,3-methylimidazole mesylate, 1,3-methylimidazole tosilate, 1-ethyl-3-methyllimidazolium bromide, iodate 1-ethyl-3-methylimidazole, iodate 1-vinyl-3-Methylimidazole., bromination 1-vinyl-3-Methylimidazole., 1-vinyl-3-Methylimidazole. perchlorate, 1-vinyl-3-methylimidazolium nitrate, 1-vinyl-3-N-Methylimidazoleacetic salt, 1-vinyl-3-Methylimidazole. tosilate, 1-vinyl-3-methyl imidazolium tetrafluoroborate, 1-propyl group-3-Methylimidazole. perchlorate, 1-propyl group-3-methyl imidazolium tetrafluoroborate, 1-propyl group-3-methylimidazolium nitrate, 1-propyl group-3-N-Methylimidazoleacetic salt, one in 1-propyl group-3-Methylimidazole. tosilate。

28. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 25, it is characterised in that described hydrophilic pyridine ionic liquid comprises the one in bromination N-ethylpyridine, ethiodide pyridine, N-ethylpyridine tetrafluoroborate, N-ethylpyridine four fluorophosphate, N-butylpyridinium Chloride, bromination N-butyl-pyridinium, N-butyl-pyridinium tetrafluoroborate, N-butyl-pyridinium mesylate, chlorination N-butyl-3-picoline, bromination N-butyl-3-picoline, N-butyl-3-picoline tetrafluoroborate。

29. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 25, it is characterized in that hydrophilic pyrrole ionic liquid comprises chlorination N-methyl, butyl pyrrolidine, ethanaminium, N-methvl, butyl pyrrolidine, N-methyl, butyl pyrrolidine fluoroform sulphonate, N-methyl, butyl pyrrolidine mesylate, N-methyl, butyl pyrrolidine tetrafluoroborate, ethanaminium, N-methvl, propyl pyrrole alkane, ethanaminium, N-methvl, ethyl pyrrolidine, N-methyl, ethyl pyrrolidine mesylate, 1-normal-butyl-1-crassitude two (trimethyl fluoride sulfonyl) acid imide, one in N-butyl-pyridinium tetrafluoroborate。

30. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 25, it is characterised in that the solvent in the mixed electrolytic solution of described cyclic carbonate electrolyte, linear carbonate electrolyte, cyclic carbonate and linear carbonate composition comprises the one in dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethylene carbonate, Allyl carbonate；Solute comprises LiClO₄、LiPF₆、LiAsF₆、LiBF₄、NaClO₄、LiCl、MgClO₄、KClO₄、NH₄ClO₄、NaNO₃、KNO₃、Al(NO₃)₃、Mg(NO₃)₂、Zn(NO₃)₂In one, the weight/mass percentage composition of solute is between 0.01% to 30%, and comprises the water of mass percent 0.01% to 10% in electrolyte。

31. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterised in that described porous polymer bag or film are the bag made of polypropylene, polyethylene, polystyrene, polyester or cellulose or film。

32. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterised in that described surfactant comprises the one in polyvinylpyrrolidone, polyoxyethylene laurel ether, Tween 80, triton X-100, PluronicP123, PluronicF127, PluronicF68, dodecylbenzene sodium sulfonate, Dodecyl trimethyl ammonium chloride, sodium lauryl sulphate, stearic acid, oleic acid, lauric acid, cetyl trimethylammonium bromide, tetrabutyl ammonium bromide, 4 bromide。

33. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterised in that the concentration of described aqueous surfactant solution is between 0.0001 mol/L to 0.5 mol/L。

34. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterized in that described organic solvent comprises ethanol, isopropanol, acetone, chloroform, carbon tetrachloride, oxolane, paracide, N, one in dinethylformamide, N,N-dimethylacetamide, methylformamide, methylacetamide, methyl propanamide, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, dimethyl sulfoxide, benzene,toluene,xylene, dichloromethane, acetonitrile, cyclic carbonate, linear carbonate。

35. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 34, it is characterized in that described cyclic carbonate, linear carbonate comprises the one in Allyl carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, Ethyl methyl carbonate。

36. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterised in that described stirring adopts magnetic force or mechanical agitation, and the time is 3 hours to 60 hours, whipping temp 20 degrees Celsius to 60 degrees Celsius。

37. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterized in that the frequency of described sonic oscillation is 5 KHz to 30 KHz, power is 100 watts to 1000 watts, 2 minutes to 10 hours time, temperature 20 degrees Celsius to 60 degrees Celsius；Suspension after ultrasonic is centrifuged 5 minutes to 30 minutes under the rotating speed of 500 revs/min to 3000 revs/min。

38. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterized in that solid concentration in liquid in step (1), (2), (3) and (4) is controlled between 0.01 mg/ml to 300 mg/ml by described Graphene, wherein Graphene is with carbonaceous gauge。

39. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterized in that the organic solvent of described separating-purifying comprises oxolane, tetramethylurea, Methanamide, N-METHYLFORMAMIDE, N, dinethylformamide, acetamide, N-methylacetamide, N, N-dimethyl acetylamide, N-methyl propanamide, 2-Pyrrolidone, N-Methyl pyrrolidone, pyrroles, pyridine, the one in 2-picoline, 3-picoline, 4-picoline。

40. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterised in that described stirring adopts magnetic force or mechanical agitation, and the time is 3 hours to 60 hours, whipping temp 20 degrees Celsius to 60 degrees Celsius。

41. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterized in that the frequency of described sonic oscillation is 5 KHz to 30 KHz, power is 100 watts to 1000 watts, 2 minutes to 10 hours time, temperature 20 degrees Celsius to 60 degrees Celsius；Suspension after ultrasonic is centrifuged 5 minutes to 30 minutes under 1000 revs/min to 10000 rev/min rotating speeds。

42. a kind of method being prepared Graphene by graphite raw ore electrolysis described in claim 1, it is characterized in that described centrifugal, sucking filtration or filter pressing comprise average pore size porous polymer bag between 0.2 micron to 20 micron or film, solid is stayed in bag, and liquid is thrown out of, extrudes, extrudes or flows out。

43. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 42, it is characterised in that porous polymer bag or film are the bag made of polypropylene, polyethylene, polystyrene, polyester or cellulose or film。

44. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterised in that described alkaline aqueous solution is NaOH or NH₃·H₂The aqueous solution of O, acidic aqueous solution is HCl/water solution。

45. a kind of method being prepared Graphene by graphite raw ore electrolysis as claimed in claim 1, it is characterised in that described drying is to adopt-50 degrees Celsius of lyophilizations, and drying time is 10 hours to 96 hours, it is thus achieved that present the graphene powder of metallochrome；Adopting air blast or vacuum drying, temperature is 70 degrees Celsius to 120 degrees Celsius, and drying time is 2 hours to 96 hours, it is thus achieved that present the graphene powder of metallochrome。