CN104264179A

CN104264179A - Method for preparing graphene from raw graphite ores through electrolysis

Info

Publication number: CN104264179A
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: 2015-01-07
Anticipated expiration: 2034-09-17
Also published as: CN104264179B

Abstract

The invention discloses a method for preparing graphene from raw graphite ores through electrolysis. The method comprises the steps of crushing raw microcrystal graphite ores, sieving, and recycling raw materials which are not insufficiently crushed; preparing an electrode from raw microcrystal graphite ore powder or insufficiently-delaminated raw ores; electrolyzing the prepared electrode in an electrolytic tank, carrying out solid-liquid separation, and further delaminating a solid obtained by separation to obtain the insufficiently-delaminated raw ores and coarsely-prepared graphene; and separating and extracting graphene from the coarsely-prepared graphene. The method has the advantages of low cost, simple preparation process and device, simplicity in operation, good product quality, high process safety and large-scale production.

Description

A kind of method being prepared Graphene by graphite raw ore electrolytic process

Technical field

The present invention relates to a kind of preparation method of Graphene, particularly a kind of method directly being prepared Graphene by graphite raw ore electrolytic process.

Background technology

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

Large-scale low-cost prepares the method for high-quality Graphene, is one of key of the investigation and application of Graphene.In recent years, many scholars are devoted to the preparation method exploring single or multiple lift Graphene, the preparation method of Graphene known at present mainly contains two classes, one class take graphite as the stripping method from top to bottom of raw material, as the oxidation reduction process (as Hummers method) etc. that mechanically peel method, graphene oxide transform, another kind of be with containing carbon compound for carbon source to be converted into the method from bottom to top of Graphene, as chemical Vapor deposition process, SiC vacuum thermal cracking method, epitaxial growth method etc. through Overheating Treatment.Wherein first kind method is that raw material has abundant advantage with graphite, because graphite mineral reserve resource reserve is huge on the earth, 70% in China.Graphite oxide reduction method is the minimum and graphene preparation method of the most easily accomplishing scale production of current cost.Graphite oxide reduction method is that natural graphite and strong acid and Strong oxdiative substance reaction are generated graphite oxide (GO), be prepared into graphene oxide (mono-layer graphite oxide) through ultrasonic disperse, the oxy radical adding reductive 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; Its shortcoming also has in redox process in addition, 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 has simply, economical, without destructiveness, environmental friendliness, the advantage that can operate at normal temperatures and pressures and the number of plies and the surface properties of Graphene can be controlled by electrode potential during adjustment intercalation-stripping, be therefore expected to the effective way becoming 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 electrolytic solution, pure graphite rod is electrode and between positive and negative electrode, applies the volts DS of 15V, and graphite anode rod is oxidized the graphene film peeled off and obtain with functionalized carbon hydrogen compound gradually.Other is using water system ionogen or strong acid as ionogen, and as using the sodium polystyrene sulfonate aqueous solution as electrolytic solution, high purity graphite rod is electrode, adds 5V direct supply and peels off and obtain Graphene (Carbon.2009,47,3242 – 3246).It is low all to there is productive rate in the Graphene product adopting above method to prepare, and the shortcomings such as defect is many, are not well positioned to 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), using propylene carbonate lithium ion as intercalating agent and combined high-strength is ultrasonic, peel off negative electrode graphite and obtain productive rate and reach more than 70%, there is the Graphene of 1-9 layer.But the method uses expensive lithium salts, and cost is high; In addition, the method lacks electrode design, and the stability of technique is bad, has short circuit thermal and cause organic solvent to burn and produce fire trouble in process of charging.Not long ago, applicant with the electrolytic solution of organic carbonate and inorganic salt for the swelling graphite of intercalation dispersion agent 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 effectively can not be applicable to crystallite (earthy, amorphous) the graphite raw ore of rich reserves.

Natural 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 median size 0.01 ~ 3mm, native floatability is better.Natural micro crystal graphite structure is made up of many small graphite crystals, and carbon content is 60% ~ 80%, and part can reach 95%, median size 0.01 ~ 1 μm, but flotability 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%, comprises SiO ₂, Al ₂o ₃, MgO, CaO, P ₂o ₅, CuO, V ₂o ₅, H ₂o, S, FeO _xand H, N, CO ₂, CH ₄, NH ₃deng.At present, the method in domestic and international purification crystalloid and aphanitic graphite ore deposit mainly contains flotation process, pyroprocess, alkali acid, hydrogen fluoride and chlorinating roasting etc.China's aphanitic graphite reserves are large, carbon 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 hydrofluoric acid of the industrial most severe toxicity of micro crystal graphite raw ore is purified, and causes serious environmental pollution, and be all simply be processed into the low value-added product such as aquadag.Without any being directly prepared into the patent of Graphene, paper and report.

In sum, prepare at present Graphene mainly with pure graphite for raw material, but graphite purifies out through a lot of step from graphite raw ore, complex process, seriously polluted.World's micro crystal graphite source of crude is large, and particularly China's reserves (as Hunan and Inner Mongol etc.) proportion is large, 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 to be directly prepared into the patent of Graphene, paper and report.

Summary of the invention

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

Main innovation part of the present invention is: directly prepare Graphene with micro crystal graphite raw ore single stage method, purity is high, and productive rate 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 directly prepares Graphene technique by micro crystal graphite raw ore single stage method is clear and definite: the carbon content according to micro crystal graphite raw ore is high, good conductivity and can ion insertion electrochemical principle and directly prepare Graphene; The separation and Extraction Graphene according to the physical and chemical principle of the conductivity difference of carbon material and mineral substance and density, dissolubility difference, on the basis of these two theoretical foundations, in laboratory practices, propose the principle model of micro crystal graphite raw ore electrochemical intercalation-leafing-separation, and realize technical process prepared by Graphene.

The present invention is by the following technical solutions:

Micro crystal graphite raw ore is carried out fragmentation and the method such as discharge and recharge and electrode fabrication assembling is applied in a flexible way.As the micro crystal graphite original ore powder after fragmentation makes porous electrode and the electrod-array of good conductivity; Can binder free when making electrode, also can add binding agent; Then with the liquid of uniqueness for electrolytic solution, adopt 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, comprise solvent dispersion, ultrasonic/stirring, centrifugal/suction filtration, washing drying treatment, obtain the Graphene of defect few, high crystallization, and part intercalator and electrolytic solution 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 and negative electrode, electrolytic solution unrestricted flow can be allowed, can prevent again anode from directly contacting with negative electrode.

The concrete technical scheme of the present invention comprises the following steps:

(1), by micro crystal graphite crushing raw ore, sieve, 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), be separated 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 comprises as follows:

The fragmentation of step described above (1) micro crystal graphite raw ore including but not limited to Mechanical Crushing, ultrasonic grinding method; After broken the particle diameter of micro crystal graphite raw ore in 10 nanometers to 5 millimeters (10nm-5mm); Can dispersion agent be added in shattering process, also can not add dispersion agent.

Described Mechanical Crushing including but not limited to ball milling, wherein more than one such as ultrasonic grinding; Ball milling ball can be the one wherein such as Stainless Steel Ball, agate ball, zirconia ball, alumina balls or silicon carbide ball; The diameter of ball is 3 millimeters to 15 millimeters (3-15mm); The material of ball grinder can be stainless steel, agate or zirconium white; 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 gas or helium; Ball-milling Time is 0.5 hour to 72 hours (0.5-72h);

Frequency 20 kilohertz ultrasonic during described ultrasonic grinding is to 30 kilohertzs (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 dispersion agent including but not limited to organic solvent, mineral acid (dense or rare), soluble inorganic alkali aqueous solution, the organic solution of soluble inorganic salt or the aqueous solution.The ratio control of dispersion agent (volume, milliliter) and micro crystal graphite raw ore (quality, gram) is between 1 ml/g to 100 mls/g (1-100ml/g).

Described organic solvent can including but not limited to N-Methyl pyrrolidone, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-METHYLFORMAMIDE, methyl-sulphoxide, benzene,toluene,xylene, chloroform, methylene dichloride, ethanol, Virahol, acetone, acetonitrile, cyclic carbonate (as propylene carbonate) or linear carbonate are (as NSC 11801, methylcarbonate, diethyl carbonate, Methyl ethyl carbonate) in one.

Described mineral acid (dense or rare) is including but not limited to H ₂sO ₄, H ₃pO ₄, HNO ₃, HClO ₄, HClO ₃one 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, NH ₃h ₂o, Na ₂cO ₃, K ₂cO ₃in one.

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

Described soluble inorganic salt is including but not limited to perchlorate, vitriol, nitrate, phosphoric acid salt, LiPF ₆, LiAsF ₆, LiBF ₄, one in LiCl.

The mass concentration of described soluble inorganic salt brine 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 comprises as follows:

As mentioned above micro crystal graphite original ore powder is made electrode to comprise micro crystal graphite breeze or not sufficiently delaminated raw ore compacting formation shaped electrode, also the micro crystal graphite original ore powder after fragmentation or not sufficiently delaminated raw ore directly can be put into polymer pouches and use as electrode.When micro crystal graphite original ore powder or not sufficiently delaminated raw ore compacting formation shaped electrode, pressure used is 1-50 MPa (1-50MPa), and press temperature can be preferably 0 degree Celsius to 400 degrees Celsius (0-400 DEG C); And the electrode of compression moulding is including but not limited to column that is membranaceous, circle or side; Can binding agent be added during electrode pressing, also can not add binding agent.Anode electrode and cathode electrode all contain the graphite content of massfraction more than 50%, and its resistivity is less than 1 kilo-ohm of momme (1K Ω m), and have hole, specific surface area is greater than 2 square meter every gram of (2m ²/ g).

The electrode of compression moulding can be self-supporting, also can add supporter.The supporter adopted can be selected from including but not limited to the one wherein such as platinum, gold and silver, copper, copper alloy, titanium, titanium alloy, graphite, plumbic oxide.Can at supporter while compacting on micro crystal graphite original ore powder or not sufficiently delaminated raw ore, also can suppress micro crystal graphite original ore powder or not sufficiently delaminated raw ore on both sides simultaneously.The thickness of the micro crystal graphite original ore powder that supporter is suppressed or not sufficiently delaminated raw ore preferably 1 millimeter to 5 millimeters (1-5mm).The optional self-contained but one be not limited in polyvinyl alcohol (PVA), Soxylat A 25-7, tetrafluoroethylene (PTFE), Xylo-Mucine (CMC), carboxymethyl cellulose, polyvinylidene difluoride (PVDF) (PVDF), urethane, resin, pitch of the binding agent that electrode pressing adopts.Ratio control between the total mass (gram) of the quality (gram) of binding agent and micro crystal graphite original ore powder or not sufficiently delaminated raw ore is between 0.01 gram/gram to 0.25 gram/gram (0.01g/g-0.25g/g).

The thickness of the columnar electrode that the self-supporting of compression moulding as above is membranaceous or square preferably 1 millimeter to 5 millimeters (1-5mm), the diameter of the columnar electrode of self-supporting circle preferably 1 millimeter to 5 millimeters (1-5mm), the optional self-contained but one be not limited in polyvinyl alcohol (PVA), Soxylat A 25-7, tetrafluoroethylene (PTFE), Xylo-Mucine (CMC), carboxymethyl cellulose, polyvinylidene difluoride (PVDF) (PVDF), urethane, resin, pitch of the binding agent that electrode pressing adopts.Ratio control between the total mass (gram) of the quality (gram) of binding agent and micro crystal graphite original ore powder or not sufficiently delaminated raw ore is between 0.01 gram/gram to 0.25 gram/gram (0.01g/g-0.25g/g).

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

The electrod-array that electrolyzer as above forms including, but not limited to multiple electrode, multiple electrolyzer forms cell array again.Each electrolyzer independently by single Power supply, also can be able to be together in parallel by single Power supply.Multiple electrolyzer may need multiple Power supply.The AC power of power supply can be direct supply also can be frequency modulation.Multiple electrolyzer is easy to structure, is convenient to expanding production of upgrading.The spacing of anode electrode and cathode electrode is between 1 millimeter to 50 millimeters (1-50mm), use between anode electrode and cathode electrode including, but not limited to porous insulation polymkeric substance (as polypropylene) bag or intermembranous every, the mean pore size of porous polymer bag or film is between 0.2 micron to 20 microns (0.2-20 μm).

4 volts of direct currents to 10 volts (4-10V) or voltage of alternating current 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); Electrolytic solution can adopt aqueous electrolyte or non-aqueous electrolyte; The ratio control of electrolytic solution (volume, milliliter) and electrode (quality, gram) is between 1 ml/g to 100 mls/g (1-100ml/g).

Wherein more than one such as the polar solvent in electrolytic solution, solvated ion, electrolyte ion, electrochemical reaction product 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, generate new product at electrode atom interlayer.This product can be gaseous state, also can be solid-state.They can stop the recovery of graphite state.The solid phase interface phase (SEI) of electrode surface has variform, and as vesica shape and particulate state, but they can be removed by subsequent disposal.

In the method described above through appropriate design and assembling electrode sequence in, each electrode can obtain in charge and discharge process electrolyte layers from, sequencing discharge and recharge had both made electrode by sufficient electrolysis, the abundant intercalation of intercalator is between the atomic shell of electrode, side reaction is effectively suppressed, and in turn ensure that the security of electrolytic reaction.The temperature of whole electrolysis system is controlled between 20 degrees Celsius to 60 degrees Celsius (20-60 DEG C), and security and the validity of reaction are further strengthened.The electrolytic solution molecule of polarization and charged ion enter between the atomic shell of electrode under curtage drives, but electric charge changes, there is chemical reaction and be trapped in electrode atom interlayer, or generate solid phase interface phase (SEI) or produce gas simultaneously, form air pressure and duct, be convenient to the further insertion of liquid-flow and intercalator and the sufficiently delaminated of electrode.

Current density can by the output voltage control of the resistance of electrolyzer system and power supply, and also can be controlled by power supply itself, current density and charge volume can regulate and control the ratio of electrode quality.The rising of electrolysis temperature is conducive to ion flow, accelerates electrolysis effectiveness.But the too high meeting of temperature causes fire to suffer from, and brings safety problem, so temperature controls below 60 DEG C.

Described aqueous electrolyte is including but not limited to HCl, HNO ₃, H ₂sO ₄, HClO ₄, HClO ₃s, NaOH aqueous solution, the KOH aqueous solution, Na ₂cO ₃the aqueous solution, K ₂cO ₃the aqueous solution, the soluble sulphate aqueous solution, the soluble nitrate aqueous solution, soluble phosphoric acid salt brine solution, solubility perchlorate aqueous solution; In the aqueous solution, the concentration of solute is between 0.01 mg/ml to 300 mg/ml (0.01-300mg/ml).

The electrolytic solution of described non-water system including but not limited to wetting ability glyoxaline ion liquid, wetting ability pyridine ionic liquid, wetting ability pyrrole ionic liquid, cyclic carbonate electrolytic solution, linear carbonate electrolytic solution, cyclic carbonate and linear carbonate composition mixed electrolytic solution in one.

Described wetting ability glyoxaline ion liquid, wetting ability pyridine ionic liquid, wetting ability 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 that glyoxaline ion liquid, pyridine ionic liquid or pyrrole ionic liquid and water form, the mass percentage of water is between 0.001% to 20% (0.001-20%).

Solvent in the mixed electrolytic solution of described cyclic carbonate electrolytic solution, linear carbonate electrolytic solution, cyclic carbonate and linear carbonate composition can including but not limited to the one in methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, NSC 11801, propylene carbonate; Solute can including but not limited to LiClO ₄, LiPF ₆, LiAsF ₆, LiBF ₄, NaClO ₄, LiCl, MgClO ₄, KClO ₄, NH ₄clO ₄, NaNO ₃, KNO ₃, Al (NO ₃) ₃, Mg (NO ₃) ₂, Zn (NO ₃) ₂in one.The mass percentage (0.01-30%) between 0.01% to 30% of solute, and in electrolytic solution, comprise the water of mass percent 0.01% to 10% (0.01-10%).

Glyoxaline ion liquid as above is including but not limited to iodate 1,3-methylimidazole, 1,3-methylimidazole methyl sulfate salt, 1,3-methylimidazole dimethyl phosphate salt, 1,3-methylimidazole a tetrafluoro borate, 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, wetting ability pyridine ionic liquid is including but not limited to bromination N-ethylpyridine, ethiodide pyridine, N-ethylpyridine a tetrafluoro borate, N-ethylpyridine four fluorophosphate, N-butylpyridinium Chloride, bromination N-butyl-pyridinium, N-butyl-pyridinium a tetrafluoro borate, N-butyl-pyridinium mesylate, chlorination N-butyl-3-picoline, bromination N-butyl-3-picoline, one in N-butyl-3-picoline a tetrafluoro borate, wetting ability 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 a tetrafluoro borate, 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) imide, one in N-butyl-pyridinium a tetrafluoro borate.

In the method described above, the solid-liquid separation of electrolysis rear electrode and electrolytic solution uses including, but not limited to mean pore size porous polymer (as polypropylene, polyethylene, polystyrene, polyester and the Mierocrystalline cellulose) bag of (0.2-20 μm) or film between 0.2 micron to 20 microns.Porous polymer bag is conducive to solid-liquor separation, and solid is stayed in bag, and liquid is thrown out of, extrude, extrude or flow out.

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

The further stripping of electrode described above comprise in methods such as utilizing 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 use aqueous electrolyte, wetting ability glyoxaline ion liquid electrolytic solution, wetting ability pyridine ionic liquid electrolytic solution or wetting ability pyrrole ionic liquid electrolytic solution electrolysis electrode, then peeling off further the solvent used can be water or the aqueous solution containing tensio-active agent, solid water or containing the concentration in the aqueous solution of tensio-active agent between 0.01 mg/ml to 20 mg/ml (0.01-20mg/ml); If use the electrolytic solution electrolysis electrode containing ring-type or linear carbonate, then peeling off the solvent used further can be organic solvent, and solid concentration is in organic solvent between 0.01 mg/ml to 20 mg/ml (0.01-20mg/ml).

Described tensio-active agent can including but not limited to the one in polyvinylpyrrolidone, polyoxyethylene laurel ether, tween 80, triton X-100, Pluronic P123, Pluronic F127, Pluronic F68, Sodium dodecylbenzene sulfonate, Trimethyllaurylammonium bromide, sodium lauryl sulphate, stearic acid, oleic acid, lauric acid, cetyl trimethylammonium bromide, Tetrabutyl amonium bromide, 4 bromide.

The concentration of described water phase surfactant mixture 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 use ethanol, Virahol, acetone, chloroform, tetracol phenixin, tetrahydrofuran (THF), santochlor, N, one in dinethylformamide, N,N-dimethylacetamide, methylformamide, methylacetamide, methyl propanamide, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, methyl-sulphoxide, benzene,toluene,xylene, methylene dichloride, acetonitrile, cyclic carbonate, linear carbonate.

Described ring-type is or/and linear carbonate can including but not limited to the one in propylene carbonate, methylcarbonate, diethyl carbonate, NSC 11801, Methyl ethyl carbonate.

Described stirring adopts magnetic force or/mechanical stirring, 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 that 5 kilohertzs are to 30 kilohertzs (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 liquid after ultrasonic is centrifugal 5 minutes to 30 minutes (5-30min) under 500 revs/min of rotating speeds to 3000 revs/min (500-3000rpm);

Five, step (5) concrete technology comprises 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 and impurity density, solvability and capillary difference tentatively to realize being separated of Graphene and solid impurity; (2) by solid obtained for step (1) alkalescence (such as NaOH, NH ₃h ₂the O aqueous solution) solution washing removes surperficial solid phase impurity; (3) by acid (such as the HCl aqueous solution) aqueous solution washing neutralization of the solid product after alkali cleaning, and hydrogen ion is utilized to replace other remaining non-carbon ion (such as sodium ion) further; (4) by the solid matter with deionized water after alkali cleaning, pickling or pure water.Then adopt the methods such as centrifugal, suction filtration/press filtration to realize solid-liquid separation, the further drying of gained solid obtains graphene powder.Graphene (with carbon Mass Calculation) controls between 0.01 mg/ml to 300 mg/ml (0.01-300mg/ml) the concentration of solid in liquid state in step (1), (2), (3) and (4).

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

In the method described above, the organic solvent of separating-purifying is including but not limited to use tetrahydrofuran (THF), tetramethyl-urea, methane amide, N-METHYLFORMAMIDE, N, dinethylformamide, ethanamide, N-methylacetamide, N, N-N,N-DIMETHYLACETAMIDE, 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 that 5 kilohertzs are to 30 kilohertzs (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 liquid after ultrasonic is centrifugal 5 minutes to 30 minutes (5-30min) under 1000 revs/min to 10000 revs/min (1000-10000rpm) rotating speeds;

Centrifugal, suction filtration or press filtration are including but not limited to using mean pore size porous polymer (as polypropylene, polyethylene, polystyrene, polyester and the Mierocrystalline cellulose) bag of (0.2-20 μm) or film between 0.2 micron to 20 microns as mentioned above.Porous polymer bag is conducive to solid-liquor separation, and solid is stayed in bag, and liquid is thrown out of, extrude, extrude or flow out.

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

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

The electrode during electrochemical stripping of the micro crystal graphite raw ore of technical solution of the present invention or its not sufficiently delaminated product 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 is greater than micro crystal graphite raw ore interlamellar spacing including but not limited to product graphene layer spacing in its microtexture.

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

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 electrolytic solution intercalation between the atomic shell 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 between the atomic shell 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 between the atomic shell of micro crystal graphite raw ore or its not sufficiently delaminated product.

Including but not limited to electrolytic solution 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 is including but not limited to wherein more than one such as chlorine element, oxygen element, protium, carbon, nitrogen element, sodium element, element silicon, phosphoric, potassium element and aluminium element.

The intercalation compound composition of technical solution of the present invention is including but not limited to ion, as perchlorate, sulfate ion, ammonium radical ion, also may including but not limited to the one wherein such as ion of the ion of the ion of sodium ion, aluminum ion, nitrate ion, phosphate anion, carbonate solvent, ion liquid solvent and water solvent.

The intercalation compound composition of technical solution of the present invention including but not limited to electrolytic solution, solid phase interface phase (SEI), gas, hydrocarbon oxygen compound, wherein more than one such as solvated ion.

The Graphene that in technical solution of the present invention, defect is few was greater than for 80% (namely Graphene product is greater than 80% to the ratio of graphite in micro crystal graphite raw ore raw material) including but not limited to Graphene productive rate, the carbon content of Graphene is greater than 98%, and the Graphene that defect is few also comprises to be drawn together but the Graphene number of plies being not limited to more than 80% is the Graphene of 1-4 atomic shell.

Prepared graphene powder supersound process in all kinds of SOLVENTS, obtain the dispersion system as prepared Chinese ink shape, 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 film, the electroconductibility of the graphene film that about 20 microns (20 μm) are thick can reach 10 ohm meters (10 Ω m), the height of the quality of Graphene as can be seen here.

By showing the statistical study of Graphene product and a large amount of sample of micro crystal graphite raw ore raw material, the intensity at (002) peak of the Graphene that different electrolytes system obtains relative to the strength ratio of micro crystal graphite raw ore between 0.1%-3%, this also illustrates micro crystal graphite raw ore laminate structure and be destroyed the lack of alignment obtaining Graphene, the productive rate (namely Graphene product is greater than 80% to the ratio of graphite in micro crystal graphite raw ore raw material) more than 80% of Graphene.

The SEM photo of this technique typical micro crystal graphite raw ore used and prepared Graphene product is shown in (Fig. 2 a, b).Graphene is mainly based on aggregate, and Graphene monolithic size only has hundreds of nanometer, very evenly, also thin than ultrathin carbon films.Further statistical study through TEM and Raman spectrum shows, Graphene accounts for the overwhelming majority with 1-4 layer, and its mass percentage accounts for more than 80% of Graphene product total mass.Graphene aggregate in this technique refers to a kind of state that Graphene is assembled.The full spectrum analysis of x-ray photoelectron power spectrum (XPS) of micro crystal graphite raw ore and Graphene final product is as (Fig. 2 c, d).As can be seen from the figure, except containing except C, O element in micro crystal graphite raw ore, also containing elements such as Si, Al, Cl.In addition, in Graphene product, C/O atom (C/O=45) is than far above C/O atomic ratio (C/O=6) in micro crystal graphite raw ore, believes that oxygen mainly comes from the absorption of Graphene to 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 be separated clean with Graphene.From TG and infrared spectrogram (Fig. 2 e of micro crystal graphite raw ore and Graphene, f) can find out on, the carbon content (>98wt%) of the after product Graphene of purification is significantly improved than the carbon content (80-90wt%) of micro crystal graphite raw ore.After repeatedly washing, obvious organo-functional group do not detected in product Graphene, illustrated that washing methods of the present invention effectively can remove byproduct of reaction, realized effectively being separated of product Graphene and impurity in micro crystal graphite raw ore.

Raman (Raman) spectrum is the powerful characterizing Graphene quality.Raman (Raman) spectrogram of typical Graphene is shown in Fig. 3.(D band, position is at 1342cm at D peak ^-1near) very weak, G peak position is at 1572cm ^-1near, low nearly 1 order of magnitude of Graphene that D peak is more standby than Hummers legal system 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 shell (Fig. 3 b).

Fig. 4 gives typical Graphene TEM photo and electron diffraction pattern pattern analysis, and Graphene is the Graphene of high crystallization, shows the sp of Graphene ²the crystalline structure of chemical bond is intact, i.e. sp ²carbon crystal layer be saved, defect is few.Internal layer 6 bright spots are suitable with the mean flow rate of 6 bright spots of time internal layer, and explanation is the Graphene of 1-4 layer, high crystallization.

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

The present invention compared with prior art tool has the following advantages:

1, the graphene powder adopting this technique to prepare can be compacted (10-15 normal atmosphere), and the two electrical measurement four-point probe measurement of resistance is less than 2.0 ohm, Graphene height 1-2 order of magnitude that its electroconductibility is more standby than Hummers legal system.

2, this technique major part dispersion agent, solvent and electrolytic solution can use by iterative cycles, 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 prepared of this technique is good, and defect is few, good conductivity.

5, present invention achieves the application of Graphene product in lithium ion battery, electrode material for super capacitor, 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. the schematic diagram of the electrode that (a) micro crystal graphite raw ore is made and electrolyzer, the schematic diagram of (b) electrolytic solution intercalation between micro crystal graphite raw ore atomic shell.

Fig. 2. the SEM photo of (a) micro crystal graphite raw ore, the SEM photo of (b) Graphene, the light ray electronic spectrum wide range of (c) micro crystal graphite raw ore and Graphene, d the carbon C1s of the x-ray photoelectron power spectrum of () micro crystal graphite raw ore and Graphene composes, (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, (f) two electron diffraction pattern of layer graphene, the electron diffraction pattern of (g) 3-4 layer graphene.

Embodiment

Embodiment 1:

(1) by 50.0g diameter be the agate ball abrading-ball of 1-1.3cm, ball grinder, to be then placed on planetary ball mill in agate jar and with the rotating speed ball milling 2 hours of 580rpm at argon shield lower seal by 1.0g micro crystal graphite raw ore and 80ml dispersion agent.With tweezers, agate ball is taken out.Dispersion agent is 70wt%HClO ₄the aqueous solution, the ratio of dispersion agent and micro crystal graphite raw ore raw material is 80ml/g.After ball milling, the median size of micro crystal graphite raw ore is at 30 μm.(2) the micro crystal graphite original ore powder after ball milling is directly loaded in polyethylene bag, make anode and negative electrode.Distance between anode and negative electrode is 5mm, and the mean pore size of polyethylene bag is 0.2 μm.(3) apply the volts DS of+5V to-5V between the anode and cathode, electrolysis 120h, exchange one-time electrode every 10h, electrolysis temperature controls at 25 DEG C.Electrolytic solution is the LiClO of 10mg/ml ₄the aqueous solution.In electrolytic solution and electrode, the ratio of graphite content total mass is 10ml/g.After electrolysis terminates, use the polyethylene bag in 10 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is thrown out of.(4) solid dispersal solid-liquid separation obtained is ultrasonic in deionized water.Ultrasonic frequency is the frequency of 5KHz, and power density is 100w, time 10h, temperature 25 DEG C.Solid concentration is in deionized water 0.1mg/ml.Then the centrifugal 30min of the rotating speed of 1000rpm is adopted to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) rough graphene dispersion is ultrasonic in deionized water.Ultrasonic frequency is 5KHz, and power density is 100w, time 10h, ultrasonic temperature 20 DEG C.By the suspension liquid centrifugal 30min under the rotating speed of 1000rpm after ultrasonic.The centrifugal solid obtained uses alkalescence (NaOH of 0.01mol/L) to wash successively, acid (HCl of 0.005mol/L) washes and deionized water washs 6 times respectively.In washing, the concentration of Graphene (with carbon Mass Calculation) is 0.1mg/ml.Then adopt polypropylene screen (0.5 μm, aperture) suction filtration, 100 DEG C of dry 24h, collect Graphene sample.The productive rate 81% of Graphene, carbon content is greater than 99% (XPS detection), in sample 85% Graphene number of plies 1-4 atomic shell (comprehensive detection).

Embodiment 2:

(1) by 50.0g diameter be the agate ball abrading-ball of 1-1.3cm, ball grinder, to be then placed on planetary ball mill in agate jar and with the rotating speed ball milling 2 hours of 580rpm at argon shield lower seal by 1.0g micro crystal graphite raw ore and 80ml dispersion agent.With tweezers, agate ball is taken out.Dispersion agent is 10wt%H ₂sO ₄the aqueous solution, the ratio of dispersion agent and micro crystal graphite raw ore raw material is 80ml/g.After ball milling, the median size of micro crystal graphite raw ore is at 30 μm.(2) the micro crystal graphite original ore powder after ball milling is directly loaded in polyethylene bag, make anode and negative electrode.Distance between anode and negative electrode is 5mm, and the mean pore size of polyethylene bag is 0.2 μm.(3) apply the volts DS of+8V to-8V between the anode and cathode, electrolysis 60h, exchange one-time electrode every 3h, electrolysis temperature controls at 40 DEG C.Electrolytic solution is the H of 100mg/ml ₂sO ₄the aqueous solution.In electrolytic solution and electrode, the ratio of graphite content total mass is 100ml/g.After electrolysis terminates, use the polyethylene bag in 0.2 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is extruded.(4) solid dispersal solid-liquid separation obtained is ultrasonic in deionized water.Ultrasonic frequency is 10KHz, and power density is 300w, time 3h, temperature 40 DEG C.Solid concentration is in deionized water 5mg/ml.Then the centrifugal 5min of the rotating speed of 3000rpm is adopted to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) rough graphene dispersion is ultrasonic in deionized water.Ultrasonic frequency is 15KHz, and power density is 500w, time 25min, temperature 40 DEG C.By the suspension liquid centrifugal 20min under the rotating speed of 7000rpm after ultrasonic.The centrifugal solid obtained uses alkalescence (the NaOH aqueous solution of pH=11) to wash successively, acid (the HCl aqueous solution of pH=4) is washed and deionized water respectively washs 6 times.In washing, the concentration of Graphene (with carbon Mass Calculation) is at 10mg/ml.Then adopt polyethylene (15 μm, aperture) bag press filtration, lyophilize 60h, collect Graphene sample.After testing, the productive rate of Graphene is greater than 84%, and carbon content is greater 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 50.0g diameter be the agate ball abrading-ball of 1-1.3cm, ball grinder, to be then placed on planetary ball mill in agate jar and with the rotating speed ball milling 2 hours of 580rpm at argon shield lower seal by 1.0g micro crystal graphite raw ore and 80ml dispersion agent.With tweezers, agate ball is taken out.Dispersion agent is 35wt%HNO ₃the aqueous solution, the ratio of dispersion agent and micro crystal graphite raw ore raw material is 80ml/g.After ball milling, the median size of micro crystal graphite raw ore is at 30 μm.(2) the micro crystal graphite original ore powder after ball milling is directly loaded in polyethylene bag, make anode and negative electrode.Distance between anode and negative electrode is 5mm, and the mean pore size of polyethylene bag is 0.2 μm.(3) apply the volts DS of+10V to-10V between the anode and cathode, electrolysis 4h, exchange one-time electrode every 30min, electrolysis temperature controls at 60 DEG C.Electrolytic solution is the Na of 300mg/ml ₂sO ₄the aqueous solution.In electrolytic solution and electrode, the ratio of graphite content total mass is 200ml/g.After electrolysis terminates, use the polyethylene bag in 5 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is forced out.(4) solid dispersal solid-liquid separation obtained, containing in the aqueous solution of P123, adopts magnetic agitation 3h, whipping temp 25 DEG C.P123 concentration is in aqueous 0.1mol/L.Solid concentration is in aqueous 5mg/ml.Then the centrifugal 10min of the rotating speed of 1000rpm is adopted to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) by rough graphene dispersion in deionized water, magnetic agitation 60h is adopted, whipping temp 20 DEG C.The Polypropylene Bag in 0.2 μm, aperture is used to realize solid-liquid separation the suspension liquid after stirring.Solid is stayed in bag, and liquid is extruded.Gained solid uses alkalescence (the NaOH aqueous solution of pH=11) to wash successively, acid (the HCl aqueous solution of pH=4) is washed and deionized water respectively washs 6 times.In washing, the concentration of Graphene (with carbon Mass Calculation) is at 30mg/ml.Then adopt Polypropylene Bag (5 μm, aperture) press filtration, lyophilize 48h, collect Graphene sample.After testing, the productive rate of Graphene is greater than 84%, and carbon content is greater 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 median size of micro crystal graphite raw ore is at 500nm.(2) electrode micro crystal graphite original ore powder after ultrasonication being 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 massfraction more than 50%, and its resistivity is 0.5 kilo-ohm of momme (0.5K Ω m), has hole, and specific surface area is 4 square meter every gram of (4m ²/ g).The pressure of electrode pressing is 5MPa, and temperature is 25 DEG C.The electrode of 8 anodes and 8 negative electrode two types forms array.The spacing of anode and negative electrode is 10mm.Adopt Polystyrene Film to separate between anode and negative electrode, the mean pore size of Polystyrene Film is 5 μm.(3) apply the voltage of alternating current of 6V between the anode and cathode, electrolysis 24h, convert primary current direction every 1min.Electrolysis temperature controls at 25 DEG C.Electrolytic solution is made up of methylcarbonate and sodium perchlorate, and the mass percentage of sodium perchlorate is 15%.The water of mass percent 1% is comprised in electrolytic solution.In electrolytic solution and electrode, the ratio of graphite content total mass is 30ml/g.After electrolysis terminates, use the polyethylene bag in 20 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is extruded.(4) solid dispersal solid-liquid separation obtained is ultrasonic in DMF (DMF).Ultrasonic frequency is 30KHz, and power density is 800w, time 4h, temperature 25 DEG C.The concentration of solid in DMF is 0.01mg/ml.Then the centrifugal 30min of the rotating speed of 500rpm is adopted to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) rough graphene dispersion is ultrasonic in DMF (DMF).Ultrasonic frequency is 10KHz, and power density is 300w, time 10min, temperature 30 DEG C.By the suspension liquid centrifugal 10min under the rotating speed of 3000rpm after ultrasonic.Used by the centrifugal solid obtained alkalescence (the NaOH aqueous solution of pH=11) to wash successively, acid (aqueous hydrochloric acid of pH=4) washes and deionized water respectively washs 5 times.In washing, the concentration of Graphene (with carbon Mass Calculation) is at 5mg/ml.Then adopt Polystyrene Film (20 μm, aperture) to filter, 70 DEG C of dry 60h, collect Graphene sample.The productive rate 85% of Graphene, carbon content 99% (XPS detection), in sample 83% Graphene number of plies 1-4 layer (comprehensive detection).

Embodiment 5:

(2) make binding agent with tetrafluoroethylene (PTFE), the columnar electrode not sufficiently delaminated raw ore being pressed into self-supporting side does anode and negative electrode, and the thickness of anode and negative electrode is 5mm.PTFE is 0.05g/g with the mass ratio of not sufficiently delaminated raw ore.Anode and negative electrode all contain the graphite content of massfraction more than 50%, and its resistivity is 0.3 kilo-ohm of momme (0.3K Ω m), has hole, specific surface area 4 square meter every gram of (4m ²/ g).The pressure of electrode pressing is 45MPa, and temperature is 80 DEG C.The electrode of anode and negative electrode two type forms array.The spacing of anode and negative electrode is at 1mm.Polypropylene screen interval is adopted between anode and negative electrode.The mean pore size of polypropylene screen is 10 μm.(3) apply the volts DS of+10V to-10V between the anode and cathode, electrolysis 48h, exchange one-time electrode every 1h.Electrolysis temperature controls at 40 DEG C.Electrolytic solution is by Al (NO ₃) ₃, LiCl and Methyl ethyl carbonate composition.The mass percentage of LiCl is 30%, Al (NO ₃) ₃mass percentage be 3%.The water of mass percent 5% is comprised in electrolytic solution.In electrolytic solution and electrode, the ratio of graphite content total mass is 50ml/g.After electrolysis terminates, use the polyethylene bag in 1 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is thrown out of.(4) solid dispersal solid-liquid separation obtained, in methylcarbonate (DMC), adopts magnetic agitation 30h, whipping temp 60 DEG C.The concentration of solid 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 that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) rough Graphene is placed in acetonitrile ultrasonic.Ultrasonic frequency is 30KHz, and power density is 800w, time 30min, temperature 30 DEG C.By the suspension liquid centrifugal 30min under the rotating speed of 10000rpm after ultrasonic.The centrifugal solid obtained uses alkalescence (the NaOH aqueous solution of pH=11) to wash successively, acid (the HCl aqueous solution of pH=4) is washed and deionized water respectively washs 6 times.In washing, the concentration of Graphene (with carbon Mass Calculation) is at 150mg/ml.Then adopt polyethylene bag (2 μm, aperture) press filtration, lyophilize 36h, collect Graphene sample.After testing, the productive rate of Graphene is greater than 84%, and carbon content is greater 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 1500.0g diameter be the agate ball abrading-ball of 1-1.3cm, 10.0g micro crystal graphite raw ore is sealed in agate jar in air atmosphere, to be then placed in by ball grinder on planetary ball mill and with the rotating speed ball milling 2 hours of 580rpm.Taken out by agate ball with tweezers, after ball milling, the median size 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 anode and negative electrode, the diameter of anode and negative electrode is 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 massfraction more than 50%, and its resistivity is 0.3 kilo-ohm of momme (0.3K Ω m), has hole, specific surface area 4 square meter every gram of (4m ²/ g).The pressure of electrode pressing is 20MPa, and temperature is 350 DEG C.The electrode of 16 anodes and 16 negative electrode two types forms array.The spacing of anode and negative electrode is at 45mm.Polypropylene Bag interval is adopted between anode and negative electrode.The mean pore size of Polypropylene Bag is 20 μm.(3) apply the volts DS of+10V to-10V between the anode and cathode, electrolysis 72h, exchange one-time electrode every 1h.Electrolysis temperature controls at 40 DEG C.Electrolytic solution is by LiPF ₆form with propylene carbonate.LiPF ₆massfraction be 5%.In electrolytic solution and electrode, the ratio of graphite content total mass is 10ml/g.After electrolysis terminates, use the polyethylene bag in 2 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is thrown out of.(4) solid dispersal solid-liquid separation obtained in propylene carbonate (PC), mechanical stirring 20h, whipping temp 30 DEG C.The concentration of solid in PC is 2mg/ml.The centrifugal 30min of rotating speed of 500rpm is adopted to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) rough graphene dispersion is ultrasonic in propylene carbonate (PC).Ultrasonic frequency is 20KHz, and power density is 500w, time 30min, temperature 25 DEG C.Suspension liquid 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) to wash successively, acid (the HCl aqueous solution of 0.005mol/L) is washed and deionized water washes 6 times respectively.In washing, the concentration of Graphene (with carbon Mass Calculation) is 50mg/ml.Then at 80 DEG C of dry 10h, Graphene sample is collected.The productive rate 85% of Graphene, carbon content is greater than 99% (XPS detection), in sample 87% Graphene number of plies 1-3 atomic shell (comprehensive detection).

Embodiment 7:

(2) make binding agent with tetrafluoroethylene (PTFE), platinized platinum is supporter, not sufficiently delaminated raw ore is compressed on the columnar electrode of side making band supporter in platinized platinum side and does anode and negative electrode.The compacting thickness of not sufficiently delaminated raw ore is 4mm.PTFE is 0.15g/g with the mass ratio of not sufficiently delaminated raw ore.Anode and negative electrode all contain the graphite content of massfraction more than 50%, and its resistivity is 0.3 kilo-ohm of momme (0.3K Ω m), has hole, specific surface area 4 square meter every gram of (4m ²/ g).The pressure of electrode pressing is 15MPa, and temperature is 150 DEG C.The electrode of anode and negative electrode two type forms array.The spacing of anode and negative electrode is at 2mm.(3) apply the volts DS of+10V to-10V between the anode and cathode, electrolysis 72h, exchange one-time electrode every 1h.Electrolysis temperature controls at 40 DEG C.Electrolytic solution is by KClO ₄, NaNO ₃form with methylcarbonate.KClO ₄mass percentage be 10%, NaNO ₃mass percentage be 1%.The water of mass percent 10% is comprised in electrolytic solution.In electrolytic solution and electrode, the ratio of graphite content total mass is 60ml/g.After electrolysis terminates, use the polyethylene bag in 0.45 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is thrown out of.(4) solid dispersal solid-liquid separation obtained is ultrasonic in tetrahydrofuran (THF) (THF).Ultrasonic frequency is 30KHz, and power density is 1000w, time 30min, temperature 25 DEG C.The concentration of solid in THF is 5mg/ml.Then the centrifugal 20min of the rotating speed of 1000rpm is adopted to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) rough Graphene is placed in methylcarbonate (DMC) ultrasonic.Ultrasonic frequency is 25KHz, and power density is 1000w, time 15min, temperature 25 DEG C.Suspension liquid after ultrasonic is centrifugal 10min under 5000rpm.The centrifugal solid obtained uses alkalescence (NaOH of 0.1mol/L) solution washing successively, acidity (the HCl aqueous solution of the 0.05mol/L) aqueous solution respectively washs 3 times and deionized water wash 6 times.In washing, the concentration of Graphene (with carbon Mass Calculation) is 300mg/ml.Then use porous polypropylene film (mean pore size of film 0.22 μm) to filter, dry 96h 80 DEG C time, then collects and detects Graphene sample.The productive rate 85% of Graphene, carbon content 99% (XPS detection), in sample 80% Graphene number of plies 1-4 layer (comprehensive detection).

Embodiment 8:

(1) pulverizer is adopted to pulverize in 10.0g micro crystal graphite raw ore.After pulverizing, the median size of micro crystal graphite raw ore is 2 μm.(2) with polyvinyl alcohol (PVA) for binding agent, the graphite paper that 5mm is thick is supporter, the micro crystal graphite original ore powder after ultrasonication is compressed on graphite paper both sides and does film-like electrode and do anode and negative electrode.The thickness of micro crystal graphite original ore powder is 1mm, PVA is 0.10g/g with the mass ratio of not sufficiently delaminated raw ore.Anode and negative electrode all contain the graphite content of massfraction more than 50%, and its resistivity is 0.5 kilo-ohm of momme (0.5K Ω m), has hole, and specific surface area is 4 square meter every gram of (4m ²/ g).The pressure of electrode pressing is 50MPa, and temperature is 25 DEG C.The electrode of 8 anodes and 8 negative electrode two types forms array.The spacing of anode and negative electrode is 5mm.Adopt Polystyrene Film to separate between anode and negative electrode, the mean pore size of Polystyrene Film is 2 μm.(3) apply the volts DS of+10V to-10V between the anode and cathode, electrolysis 12h, exchange one-time electrode every 1h.Electrolysis temperature controls at 60 DEG C.Electrolytic solution is 1,3-methylimidazole perchlorate, comprises the water of mass percent 20% in electrolytic solution.In electrolytic solution and electrode, the ratio of graphite content total mass is 10ml/g.After electrolysis terminates, use the polyethylene bag in 0.2 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is thrown out of.(4) solid dispersal solid-liquid separation obtained, containing in the aqueous solution of F127, adopts mechanical stirring 10h, whipping temp 60 DEG C.F127 concentration is in aqueous 0.01mol/L.Solid concentration is in aqueous 10mg/ml.Then the centrifugal 20min of the rotating speed of 1500rpm is adopted to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) by rough graphene dispersion in deionized water, magnetic agitation 60h is adopted, whipping temp 20 DEG C.The Polypropylene Bag in 0.2 μm, aperture is used to realize solid-liquid separation the suspension liquid after stirring.Solid is stayed in bag, and liquid is extruded.Gained solid uses alkalescence (the NaOH aqueous solution of pH=11) to wash successively, acid (the HCl aqueous solution of pH=4) is washed and deionized water respectively washs 6 times.In washing, the concentration of Graphene (with carbon Mass Calculation) is at 30mg/ml.Then adopt Polypropylene Bag (5 μm, aperture) press filtration, lyophilize 48h, collect Graphene sample.After testing, the productive rate of Graphene is greater than 84%, and carbon content is greater 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 1500.0g diameter be the zirconia ball abrading-ball of 3-8mm; ball grinder, to be then placed on planetary ball mill in zirconia ball grinding jar and with the rotating speed ball milling 30 hours of 300 revs/min at nitrogen atmosphere protection lower seal by 10.0g micro crystal graphite raw ore and 60ml dispersion agent.With tweezers, zirconia ball is taken out.Dispersion agent is made up of propylene carbonate and sodium perchlorate, and the mass percent of sodium perchlorate is 5%.The ratio of dispersion agent and micro crystal graphite raw ore is 6ml/g.After ball milling, the median size of micro crystal graphite raw ore is at 2 μm.(2) the micro crystal graphite original ore powder after ball milling is directly loaded in polyethylene bag, make anode and negative electrode.Distance between anode and negative electrode is 5mm, and the mean pore size of polyethylene bag is 0.2 μm.(3) apply the volts DS of+10V to-10V between the anode and cathode, electrolysis 72h, exchange one-time electrode every 1h.Electrolysis temperature controls at 40 DEG C.Electrolytic solution is by KClO ₄, NaNO ₃form with methylcarbonate.KClO ₄mass percentage be 10%, NaNO ₃mass percentage be 1%.The water of mass percent 10% is comprised in electrolytic solution.In electrolytic solution and electrode, the ratio of graphite content total mass is 60ml/g.After electrolysis terminates, use the polyethylene bag in 0.45 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is thrown out of.(4) solid dispersal solid-liquid separation obtained is ultrasonic in acetone.Ultrasonic frequency is 10KHz, power density 500w, time 1h, temperature 25 DEG C.Solid concentration is in acetone 10mg/ml.Then the centrifugal 20min of the rotating speed of 1000rpm is adopted to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) rough graphene dispersion is ultrasonic in 2-methyl-2-pyrrolidone.Ultrasonic frequency is 30KHz, and power density is 800w, time 5h, temperature 30 DEG C.Suspension liquid 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) to wash successively, acid (the HCl aqueous solution of 0.05mol/L) washing and each 6 times of deionized water wash.In washing, the concentration of Graphene (with carbon Mass Calculation) is 80mg/ml.Then use porous polypropylene bag (mean pore size of bag 15 μm) press filtration, lyophilize 24h, collects and detects gained Graphene sample.The product of Graphene 250 grams, carbon content 99% (XPS detection), in sample, the Graphene of more than 88% is 1-4 atomic shell (comprehensive detection).

Embodiment 10:

(1) by 1500.0g diameter be the zirconia ball abrading-ball of 3-8mm; 10.0g micro crystal graphite raw ore and 60ml dispersion agent are sealed in zirconia ball grinding jar under nitrogen protection, to be then placed in by ball grinder 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 contained in negative electrode and the anode of making electrolyzer in two polyethylene bags.Dispersion agent is by methylcarbonate and LiPF ₆composition, LiPF ₆mass percent be 2%.The ratio of dispersion agent and micro crystal graphite raw ore is 6ml/g.After ball milling, the median size of micro crystal graphite raw ore is at 2 μm.(2) the micro crystal graphite original ore powder after ball milling is directly loaded in polyethylene bag, make anode and negative electrode.Distance between anode and negative electrode is 5mm, and the mean pore size of polyethylene bag is 0.2 μm.(3) apply the volts DS of+10V to-10V between the anode and cathode, electrolysis 72h, exchange one-time electrode every 1h.Electrolysis temperature controls at 40 DEG C.Electrolytic solution is by LiPF ₆form with propylene carbonate.LiPF ₆massfraction be 5%.In electrolytic solution and electrode, the ratio of graphite content total mass is 10ml/g.After electrolysis terminates, use the polyethylene bag in 2 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is thrown out of.(4) solid dispersal solid-liquid separation obtained, in methylcarbonate (DMC), adopts magnetic agitation 30h, whipping temp 60 DEG C.The concentration of solid in DMC is 5mg/ml.Then the centrifugal 10min of the rotating speed of 2000rpm is adopted to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) rough graphene dispersion is ultrasonic in propylene carbonate.Ultrasonic frequency is 20KHz, and power density is 500w, time 30min, temperature 25 DEG C.Suspension liquid 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) to wash successively, acid (the HCl aqueous solution of 0.005mol/L) is washed and deionized water washes 6 times respectively.In washing, the concentration of Graphene (with carbon Mass Calculation) is 50mg/ml.Then at 80 DEG C of dry 10h, Graphene sample is collected.The productive rate 85% of Graphene, carbon content is greater than 99% (XPS detection), in sample 87% Graphene number of plies 1-3 atomic shell (comprehensive detection).

Embodiment 11:

(1) by 1500.0g diameter be the zirconia ball abrading-ball of 3-8mm; 10.0g micro crystal graphite raw ore and 60ml dispersion agent are sealed in zirconia ball grinding jar under nitrogen protection, to be then placed in by ball grinder on planetary ball mill and with the rotating speed ball milling 30 hours of 300 revs/min.With tweezers, zirconia ball is taken out.Dispersion agent is made up of DMF and LiCl, and the mass percent of LiCl is 5%.The ratio of dispersion agent and micro crystal graphite raw ore is 6ml/g.After ball milling, the median size of micro crystal graphite raw ore is at 2 μm.(2) the micro crystal graphite original ore powder after ball milling is directly loaded in polyethylene bag, make anode and negative electrode.Distance between anode and negative electrode is 5mm, and the mean pore size of polyethylene bag is 0.2 μm.(3) apply the volts DS of+10V to-10V between the anode and cathode, electrolysis 48h, exchange one-time electrode every 1h.Electrolysis temperature controls at 40 DEG C.Electrolytic solution is by Al (NO ₃) ₃, LiCl and Methyl ethyl carbonate composition.The mass percentage of LiCl is 30%, Al (NO ₃) ₃mass percentage be 3%.The water of mass percent 5% is comprised in electrolytic solution.In electrolytic solution and electrode, the ratio of graphite content total mass is 50ml/g.After electrolysis terminates, use the polyethylene bag in 1 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is thrown out of.(4) solid dispersal solid-liquid separation obtained, in acetonitrile, adopts magnetic agitation 60h, whipping temp 30 DEG C.The concentration of solid in acetonitrile is 20mg/ml.Then adopt the centrifugal 15min of the rotating speed of 1500rpm, obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) by rough graphene dispersion in N-Methyl pyrrolidone, adopt magnetic agitation 3h, whipping temp 60 DEG C.Suspension liquid 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) to wash successively, acid (the HCl aqueous solution of 0.005mol/L) is washed and deionized water washes 6 times respectively.In washing, the concentration of Graphene (with carbon Mass Calculation) is 100mg/ml.Then adopt polyethylene bag press filtration, 80 DEG C of dry 40h, collect Graphene sample.The productive rate 81% of Graphene, carbon content is greater than 99% (XPS detection), in sample 85% Graphene number of plies 1-4 atomic shell (comprehensive detection).

Embodiment 12:

(1) by 500.0g diameter be the alumina balls abrading-ball of 8-15mm; ball grinder, to be then placed on planetary ball mill in agate jar and with the rotating speed ball milling 60 hours of 100 revs/min at air conservation lower seal by 10.0g micro crystal graphite raw ore and 300ml dispersion agent.With tweezers, alumina balls are taken out.Dispersion agent is the NaOH aqueous solution of massfraction 20%.The ratio of dispersion agent and micro crystal graphite raw ore raw material is 30ml/g.After ball milling, the median size of micro crystal graphite raw ore is at 5 μm.(2) the micro crystal graphite original ore powder after ball milling is directly loaded in polyethylene bag, make anode and negative electrode.Distance between anode and negative electrode is 5mm, and the mean pore size of polyethylene bag is 0.2 μm.(3) apply the volts DS of+10V to-10V between the anode and cathode, electrolysis 4h, exchange one-time electrode every 30min, electrolysis temperature controls at 60 DEG C.Electrolytic solution is the Na of 300mg/ml ₂sO ₄the aqueous solution.In electrolytic solution and electrode, the ratio of graphite content total mass is 200ml/g.After electrolysis terminates, use the polyethylene bag in 5 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is thrown out of.(4) solid dispersal solid-liquid separation obtained is containing ultrasonic in the aqueous solution of F68.Ultrasonic frequency is 15KHz, and power density is 500w, time 5h, temperature 20 DEG C.F68 concentration is in aqueous 0.5mol/L.Solid concentration is in aqueous 17mg/ml.Then the centrifugal 10min of the rotating speed of 2000rpm is adopted to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) by rough graphene dispersion in deionized water, adopt mechanical stirring 30h, whipping temp 40 DEG C, then use the polyethylene bag in 10 μm, 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) to wash successively, acid (the HCl aqueous solution of pH=4) is washed and deionized water respectively washs 6 times.In washing, the concentration of Graphene (with carbon Mass Calculation) is at 50mg/L.Then adopt polyethylene film (1 μm, aperture) suction filtration, lyophilize 10h, collect Graphene sample.After testing, the productive rate of Graphene is greater than 84%, and carbon content is greater 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 500.0g diameter be the alumina balls abrading-ball of 8-15mm; ball grinder, to be then placed on planetary ball mill in agate jar and with the rotating speed ball milling 60 hours of 100 revs/min at air conservation lower seal by 10.0g micro crystal graphite raw ore and 300ml dispersion agent.With tweezers, alumina balls are taken out.Dispersion agent is the KOH aqueous solution of massfraction 2%.The ratio of dispersion agent and micro crystal graphite raw ore raw material is 30ml/g.After ball milling, the median size of micro crystal graphite raw ore is at 5 μm.(2) the micro crystal graphite original ore powder after ball milling is directly loaded in polyethylene bag, make anode and negative electrode.Distance between anode and negative electrode is 5mm, and the mean pore size of polyethylene bag is 0.2 μm.(3) apply the volts DS of+8V to-8V between the anode and cathode, electrolysis 60h, exchange one-time electrode every 3h, electrolysis temperature controls at 40 DEG C.Electrolytic solution is the H of 100mg/ml ₂sO ₄the aqueous solution.In electrolytic solution and electrode, the ratio of graphite content total mass is 100ml/g.After electrolysis terminates, use the polyethylene bag in 0.2 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is thrown out of.(4) solid dispersal solid-liquid separation obtained is ultrasonic in deionized water.Ultrasonic frequency is 10KHz, and power density is 300w, time 3h, temperature 40 DEG C.Solid concentration is in deionized water 5mg/ml.Then the centrifugal 5min of the rotating speed of 3000rpm is adopted to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(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, aperture to realize solid-liquid separation.Gained solid uses alkalescence (the NaOH aqueous solution of pH=11) to wash successively, acidity washes (aqueous hydrochloric acid of pH=5) and deionized water washs 5 times respectively.In washing, the concentration of Graphene (with carbon Mass Calculation) is at 100mg/ml.Then use (mean pore size of bag 0.2 μm) press filtration in porous polypropylene bag, when 80 DEG C, dry 48h Graphene, collects Graphene sample.The productive rate 83% of Graphene, carbon 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 500.0g diameter be the alumina balls abrading-ball of 8-15mm; ball grinder, to be then placed on planetary ball mill in agate jar and with the rotating speed ball milling 60 hours of 100 revs/min at air conservation lower seal by 10.0g micro crystal graphite raw ore and 300ml dispersion agent.With tweezers, alumina balls are taken out.Dispersion agent is the NH of massfraction 10% ₃h ₂the O aqueous solution.The ratio of dispersion agent and micro crystal graphite raw ore raw material is 30ml/g.After ball milling, the median size of micro crystal graphite raw ore is at 5 μm.(2) the micro crystal graphite original ore powder after ball milling is directly loaded in polyethylene bag, make anode and negative electrode.Distance between anode and negative electrode is 5mm, and the mean pore size of polyethylene bag is 0.2 μm.(3) apply the volts DS of+8V to-8V between the anode and cathode, electrolysis 60h, exchange one-time electrode every 3h, electrolysis temperature controls at 40 DEG C.Electrolytic solution is the H of 100mg/ml ₂sO ₄the aqueous solution.In electrolytic solution and electrode, the ratio of graphite content total mass is 100ml/g.After electrolysis terminates, use the polyethylene bag in 0.2 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is thrown out of.(4) solid dispersal solid-liquid separation obtained is ultrasonic in deionized water.Ultrasonic frequency is 5KHz, and power density is 100w, time 10h, temperature 25 DEG C.Solid concentration is in deionized water 0.1mg/ml, then adopts the centrifugal 30min of the rotating speed of 1000rpm to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) rough graphene dispersion is ultrasonic in deionized water.Ultrasonic frequency is 15KHz, and power density is 500w, time 20min, temperature 20 DEG C.Suspension liquid 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) to wash successively, acid (the HCl aqueous solution of 0.005mol/L) is washed and deionized water washes 6 times respectively.In washing, the concentration of Graphene (with carbon Mass Calculation) is 20mg/ml.Then adopt polyethylene film (1 μm, aperture) suction filtration, 120 DEG C of dry 10h, collect Graphene sample.The productive rate 81% of Graphene, carbon content is greater than 99% (XPS detection), in sample 90% Graphene number of plies 1-4 atomic shell (comprehensive detection).

Embodiment 15:

(1) 20.0g micro crystal graphite raw ore is adopted ultrasonic grinding together with 60ml dispersion agent.Ultrasonic frequency is 20KHz, power density 500w, time 28h, temperature 25 DEG C.Dispersion agent is the aluminum nitrate aqueous solution of massfraction 8%.The ratio of dispersion agent and micro crystal graphite raw ore raw material is 3ml/g.After pulverizing, the median size of micro crystal graphite raw ore is 3mm.(2) electrode micro crystal graphite original ore powder after ultrasonication being 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 massfraction more than 50%, its resistivity is 0.5 kilo-ohm of momme (0.5K Ω m), have hole, specific surface area is 4 square meter every gram of (4m ²/ g).The pressure of electrode pressing is 5MPa, and temperature is 25 DEG C.The electrode of 8 anodes and 8 negative electrode two types forms array.The spacing of anode and negative electrode is 10mm.Adopt Polystyrene Film to separate between anode and negative electrode, the mean pore size of Polystyrene Film is 5 μm.(3) apply the volts DS of+9V to-9V between the anode and cathode, electrolysis 12h, exchange one-time electrode every 1h.Electrolysis temperature controls at 60 DEG C.Electrolytic solution is N-ethylpyridine a tetrafluoro borate.The water of mass percent 10% is comprised in electrolytic solution.In electrolytic solution and electrode, the ratio of graphite content total mass is 50ml/g.After electrolysis terminates, use the polyethylene bag in 0.2 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is thrown out of.(4) solid dispersal solid-liquid separation obtained is ultrasonic in deionized water.Ultrasonic frequency is 10KHz, and power density is 300w, time 3h, temperature 40 DEG C.Solid concentration is in deionized water 5mg/ml.Then the centrifugal 5min of the rotating speed of 3000rpm is adopted to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) by rough graphene dispersion in deionized water, magnetic agitation 60h is adopted, whipping temp 30 DEG C.Suspension liquid 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) to wash successively, acid (the HCl aqueous solution of 0.005mol/L) is washed and deionized water washes 6 times respectively.In washing, the concentration of Graphene (with carbon Mass Calculation) is 300mg/ml.Then adopt polyethylene bag (1 μm, aperture) press filtration, 80 DEG C of dry 30h, collect Graphene sample.The productive rate 81% of Graphene, carbon content is greater than 99% (XPS detection), in sample 87% Graphene number of plies 1-4 atomic shell (comprehensive detection).

Embodiment 16:

(1) 1.0g micro crystal graphite raw ore is adopted ultrasonic grinding together with 80ml dispersion agent.Ultrasonic frequency is 25KHz, power density 800w, time 15h, temperature 40 DEG C.Dispersion agent is the lithium perchlorate aqueous solution of massfraction 1.5%.The ratio of dispersion agent and micro crystal graphite raw ore raw material is 80ml/g.After pulverizing, the median size of micro crystal graphite raw ore is at 500nm.(2) with polyvinyl alcohol (PVA) for binding agent, the graphite paper that 5mm is thick is supporter, the micro crystal graphite original ore powder after ultrasonication is compressed on graphite paper both sides and does film-like electrode and do anode and negative electrode.The thickness of micro crystal graphite original ore powder is the mass ratio of 1mm, PVA and micro crystal graphite original ore powder is 0.10g/g.Anode and negative electrode all contain the graphite content of massfraction more than 50%, and its resistivity is 0.5 kilo-ohm of momme (0.5K Ω m), has hole, and specific surface area is 4 square meter every gram of (4m ²/ g).The pressure of electrode pressing is 50MPa, and temperature is 25 DEG C.The electrode of 8 anodes and 8 negative electrode two types forms array.The spacing of anode and negative electrode is 5mm.Adopt Polystyrene Film to separate between anode and negative electrode, the mean pore size of Polystyrene Film is 2 μm.(3) apply the voltage of alternating current of 10V between the anode and cathode, electrolysis 30h, convert primary current direction every 30min.Electrolysis temperature controls at 60 DEG C.Electrolytic solution is 1-normal-butyl-1-crassitude two (trimethyl fluoride sulfonyl) imide.The water of mass percent 1% is comprised in electrolytic solution.In electrolytic solution and electrode, the ratio of graphite content total mass is 20ml/g.After electrolysis terminates, use the polyethylene bag in 0.2 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is thrown out of.(4) solid dispersal solid-liquid separation obtained is ultrasonic in deionized water.Ultrasonic frequency is 5KHz, and power density is 100w, time 10h, temperature 25 DEG C.Solid concentration is in deionized water 0.1mg/ml, then adopts the centrifugal 30min of the rotating speed of 1000rpm to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(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, aperture to realize solid-liquid separation.Gained solid uses alkalescence (the NaOH aqueous solution of pH=11) to wash successively, acidity washes (aqueous hydrochloric acid of pH=5) and deionized water washs 5 times respectively.In washing, the concentration of Graphene (with carbon Mass Calculation) is at 100mg/ml.Then use (mean pore size of bag 0.2 μm) press filtration in porous polypropylene bag, when 80 DEG C, dry 48h Graphene, collects Graphene sample.The productive rate 83% of Graphene, carbon 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 dispersion agent.Ultrasonic frequency is 30KHz, power density 1000w, time 2h, temperature 60 C.Dispersion agent is the aqueous sodium persulfate solution of massfraction 15%.The ratio of dispersion agent and micro crystal graphite raw ore raw material is 30ml/g.After pulverizing, micro crystal graphite raw ore median size is at 20 μm.(2) electrode micro crystal graphite original ore powder after ultrasonication being 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 massfraction more than 50%, its resistivity is 0.5 kilo-ohm of momme (0.5K Ω m), have hole, specific surface area is 4 square meter every gram of (4m ²/ g).The pressure of electrode pressing is 5MPa, and temperature is 25 DEG C.The electrode of 8 anodes and 8 negative electrode two types forms array.The spacing of anode and negative electrode is 10mm.Adopt Polystyrene Film to separate between anode and negative electrode, the mean pore size of Polystyrene Film is 5 μm.(3) apply the volts DS of+10V to-10V between the anode and cathode, electrolysis 4h, exchange one-time electrode every 30min, it is 60 DEG C that electrolysis temperature controls.Electrolytic solution is the Na of 300mg/ml ₂sO ₄the aqueous solution.In electrolytic solution and electrode, the ratio of graphite content total mass is 200ml/g.After electrolysis terminates, use the polyethylene bag in 5 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is thrown out of.(4) solid dispersal solid-liquid separation obtained is ultrasonic in deionized water.Ultrasonic frequency is 10KHz, and power density is 300w, time 3h, temperature 40 DEG C.Solid concentration is in deionized water 5mg/ml.Then the centrifugal 5min of the rotating speed of 3000rpm is adopted to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) by rough graphene dispersion in deionized water, adopt mechanical stirring 30h, whipping temp 40 DEG C, then use the polyethylene bag in 10 μm, 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) to wash successively, acid (the HCl aqueous solution of pH=4) is washed and deionized water respectively washs 6 times.In washing, the concentration of Graphene (with carbon Mass Calculation) is at 50mg/ml.Then adopt polyethylene film (1 μm, aperture) suction filtration, lyophilize 10h, collect Graphene sample.After testing, the productive rate of Graphene is greater than 84%, and carbon content is greater 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 tetrafluoroethylene (PTFE), the columnar electrode not sufficiently delaminated raw ore being pressed into self-supporting side does anode and negative electrode, and the thickness of anode and negative electrode is 5mm.PTFE is 0.05g/g with the mass ratio of not sufficiently delaminated raw ore.Anode and negative electrode all contain the graphite content of massfraction more than 50%, and its resistivity is 0.3 kilo-ohm of momme (0.3K Ω m), has hole, specific surface area 4 square meter every gram of (4m ²/ g).The pressure of electrode pressing is 45MPa, and temperature is 80 DEG C.The electrode of anode and negative electrode two type forms array.The spacing of anode and negative electrode is at 1mm.Polypropylene screen interval is adopted between anode and negative electrode.The mean pore size of polypropylene screen is 10 μm.(3) apply the volts DS of+10V to-10V between the anode and cathode, electrolysis 72h, exchange one-time electrode every 1h.Electrolysis temperature controls at 40 DEG C.Electrolytic solution is by LiPF ₆form with propylene carbonate.LiPF ₆massfraction be 5%.In electrolytic solution and electrode, the ratio of graphite content total mass is 10ml/g.After electrolysis terminates, use the polyethylene bag in 2 μm, aperture to realize solid and be separated with electrolytic solution.Solid is stayed in bag, and electrolytic solution is thrown out of.(4) solid dispersal solid-liquid separation obtained, in Methyl ethyl carbonate, adopts magnetic agitation 15h, whipping temp 40 DEG C.The concentration of solid in Methyl ethyl carbonate is 5mg/ml.The centrifugal 10min of rotating speed of 1500rpm is adopted to obtain rough Graphene and not sufficiently delaminated raw ore.The centrifugal liquid that obtains and not sufficiently delaminated raw ore are recovered utilization.(5) by rough graphene dispersion in ethanamide, adopt mechanical stirring 30h, whipping temp 60 DEG C, then adopts the centrifugal 30min of the rotating speed of 2000rpm.The centrifugal solid obtained uses alkalescence (the NaOH aqueous solution of 0.01mol/L) to wash successively, acid (the HCl aqueous solution of 0.005mol/L) is washed and deionized water washes 6 times respectively.In washing, the concentration of Graphene (with carbon Mass Calculation) is 200mg/ml.Then adopt polystyrene bag (10 μm, aperture) press filtration, 120 DEG C of dry 10h, collect Graphene sample.The productive rate 81% of Graphene, carbon content is greater than 99% (XPS detection), in sample 85% Graphene number of plies 1-3 atomic shell (comprehensive detection).

Claims

1. prepared a method for Graphene by graphite raw ore electrolytic process, it is characterized in that comprising the following steps:

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

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

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

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

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

2. a kind of method being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 1, is characterized in that the fragmentation of described step (1) micro crystal graphite raw ore is including but not limited to Mechanical Crushing, ultrasonic grinding method; After broken the particle diameter of micro crystal graphite raw ore in 10 nanometers to 5 millimeters; Add dispersion agent in shattering process, or do not add dispersion agent.

3. a kind of method being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 2, is characterized in that described Mechanical Crushing is including but not limited to ball milling.

4. a kind of method being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 3, is characterized in that the ball milling ball of described ball milling is Stainless Steel Ball, agate ball, zirconia ball, alumina balls or silicon carbide ball one wherein; The diameter of ball is 3 millimeters to 15 millimeters; The material of ball grinder is stainless steel, agate or zirconium white.

5. a kind of method being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 3, is characterized 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 gas or helium; Ball-milling Time is 0.5 hour to 72 hours.

6. a kind of method being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 2, frequency 20 kilohertz ultrasonic when it is characterized in that described ultrasonic grinding is to 30 kilohertzs, power density 500 watts to 1000 watts, 10 minutes to 30 hours time, temperature 20 degrees Celsius to 60 degrees Celsius.

7. a kind of method being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 2, it is characterized in that described dispersion agent is including but not limited to organic solvent, mineral acid, soluble inorganic alkali aqueous solution, the organic solution of soluble inorganic salt or the aqueous solution, the ratio control of dispersion agent and micro crystal graphite raw ore is between 1 ml/g to 100 mls/g.

8. a kind of method being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 7, it is characterized in that described organic solvent is including but not limited to N-Methyl pyrrolidone, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-METHYLFORMAMIDE, methyl-sulphoxide, benzene,toluene,xylene, the one in chloroform, methylene dichloride, ethanol, Virahol, acetone, acetonitrile, cyclic carbonate or linear carbonate.

9. a kind of method being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 8, it is characterized in that described cyclic carbonate is propylene carbonate, linear carbonate is NSC 11801, methylcarbonate, diethyl carbonate or Methyl ethyl carbonate.

10. a kind of method being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 7, is characterized in that described mineral acid is including but not limited to H ₂sO ₄, H ₃pO ₄, HNO ₃, HClO ₄, HClO ₃one in S.

11. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 7, is characterized in that described mineral acid mass concentration is between 1% to 98%.

12. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 7, is characterized in that described soluble inorganic alkali is including but not limited to NaOH, KOH, NH ₃h ₂o, Na ₂cO ₃, K ₂cO ₃in one.

13. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 7, is characterized in that described soluble inorganic alkali aqueous solution mass concentration is between 0.5% to 20%.

14. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 7, is characterized in that described soluble inorganic salt is including but not limited to perchlorate, vitriol, nitrate, phosphoric acid salt, LiPF ₆, LiAsF ₆, LiBF ₄, one in LiCl.

15. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 7, is characterized in that described soluble inorganic salt brine solution mass concentration is between 0.01% to 15%.

16. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 15, is characterized in that the mass concentration of described soluble inorganic salt organic solution is between 0.01% to 10%.

17. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 1, it is characterized in that micro crystal graphite original ore powder or not sufficiently delaminated raw ore are made electrode and comprised micro crystal graphite breeze or the compacting of not sufficiently delaminated raw ore are formed shaped electrode by described step (2), or the micro crystal graphite original ore powder after fragmentation or not sufficiently delaminated raw ore are directly put into polymer pouches use as electrode.

18. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 17, it is characterized in that described micro crystal graphite original ore powder or not sufficiently delaminated raw ore suppress pressure used when forming shaped electrode is 1-50 MPa, further, press temperature can be 0 degree Celsius to 400 degrees Celsius; And the electrode of compression moulding is including but not limited to column that is membranaceous, circle or side; Add binding agent during electrode pressing, or do not add binding agent.

19. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 18, is characterized in that the electrode of described compression moulding is self-supporting or adds supporter.

20. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 19, it is characterized in that the supporter of described employing is selected from including but not limited to platinum, gold and silver, copper, copper alloy, titanium, titanium alloy, graphite, plumbic oxide one wherein, 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, the thickness of the micro crystal graphite original ore powder that supporter is suppressed or not sufficiently delaminated raw ore is 1 millimeter to 5 millimeters.

21. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 19, it is characterized in that the thickness of the columnar electrode that the self-supporting of described compression moulding is membranaceous or square is 1 millimeter to 5 millimeters, the diameter of the columnar electrode of self-supporting circle is 1 millimeter to 5 millimeters.

22. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 18, is characterized in that described binding agent is including but not limited to the one in polyvinyl alcohol, Soxylat A 25-7, tetrafluoroethylene, Xylo-Mucine, carboxymethyl cellulose, polyvinylidene difluoride (PVDF), urethane, resin, pitch.

23. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 18, is characterized 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.

24. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 17, described in is characterized in that

Contain the graphite content of massfraction more than 50% in described electrode, its resistivity is less than 1 kilo-ohm of momme, and specific surface area is greater than 2 square meter every gram.

25. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 1, it is characterized in that the electrod-array that described step (3) electrolyzer forms including, but not limited to multiple electrode, multiple electrolyzer forms cell array again, each electrolyzer independently by single Power supply, also can be able to be together in parallel by single Power supply.

26. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 1, it is characterized in that the spacing of anode electrode in described step (3) electrolyzer and cathode electrode is between 1 millimeter to 50 millimeters, use between anode electrode and cathode electrode including, but not limited to porous insulation polymer pouches or intermembranous every.

27. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 26, it is characterized in that described porous polymer bag or film are that polypropylene material is made, its mean pore size is between 0.2 micron to 20 microns.

28. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 1, is characterized in that described step (3) applies direct current or the voltage of alternating current 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; Electrolytic solution adopts aqueous electrolyte or non-aqueous electrolyte; The ratio control of electrolytic solution and electrode is between 1 ml/g to 100 mls/g.

29. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 28, is characterized in that described aqueous electrolyte is including but not limited to HCl, HNO ₃, H ₂sO ₄, HClO ₄, HClO ₃s, NaOH aqueous solution, the KOH aqueous solution, Na ₂cO ₃the aqueous solution, K ₂cO ₃the aqueous solution, the soluble sulphate aqueous solution, the soluble nitrate aqueous solution, soluble phosphoric acid salt brine solution, solubility perchlorate aqueous solution; In the aqueous solution, the concentration of solute is between 0.01 mg/ml to 300 mg/ml.

30. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 28, is characterized in that the one in the mixed electrolytic solution that the electrolytic solution of described non-water system forms including but not limited to wetting ability glyoxaline ion liquid, wetting ability pyridine ionic liquid, wetting ability pyrrole ionic liquid, cyclic carbonate electrolytic solution, linear carbonate electrolytic solution, cyclic carbonate and linear carbonate.

31. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 30, it is characterized in that described wetting ability glyoxaline ion liquid, wetting ability pyridine ionic liquid, wetting ability 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 that glyoxaline ion liquid, pyridine ionic liquid or pyrrole ionic liquid and water form, the mass percentage of water is between 0.001% to 20%.

32. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 30, is characterized in that described wetting ability glyoxaline ion liquid is including but not limited to iodate 1,3-methylimidazole, 1,3-methylimidazole methyl sulfate salt, 1,3-methylimidazole dimethyl phosphate salt, 1,3-methylimidazole a tetrafluoro borate, 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.

33. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 30, is characterized in that described wetting ability pyridine ionic liquid is including but not limited to the one in bromination N-ethylpyridine, ethiodide pyridine, N-ethylpyridine a tetrafluoro borate, N-ethylpyridine four fluorophosphate, N-butylpyridinium Chloride, bromination N-butyl-pyridinium, N-butyl-pyridinium a tetrafluoro borate, N-butyl-pyridinium mesylate, chlorination N-butyl-3-picoline, bromination N-butyl-3-picoline, N-butyl-3-picoline a tetrafluoro borate.

34. a kind of method being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 30, it is characterized in that wetting ability 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 a tetrafluoro borate, 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) imide, one in N-butyl-pyridinium a tetrafluoro borate.

35. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 30, is characterized in that solvent in the mixed electrolytic solution that described cyclic carbonate electrolytic solution, linear carbonate electrolytic solution, cyclic carbonate and linear carbonate form is including but not limited to the one in methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, NSC 11801, propylene carbonate; Solute is including but not limited to LiClO ₄, LiPF ₆, LiAsF ₆, LiBF ₄, NaClO ₄, LiCl, MgClO ₄, KClO ₄, NH ₄clO ₄, NaNO ₃, KNO ₃, Al (NO ₃) ₃, Mg (NO ₃) ₂, Zn (NO ₃) ₂in one, the mass percentage of solute between 0.01% to 30%, and comprises the water of mass percent 0.01% to 10% in electrolytic solution.

36. a kind of method being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 1, it is characterized in that the solid-liquid separation of electrolysis rear electrode and electrolytic solution in described step (3) uses including, but not limited to porous polymer (as polypropylene, polyethylene, polystyrene, polyester and the Mierocrystalline cellulose) bag of mean pore size between 0.2 micron to 20 microns or film, solid is stayed in bag, and liquid is thrown out of, extrude, extrude or flow out.

37. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 36, is characterized in that described porous polymer bag or film are the bag or film made as polypropylene, polyethylene, polystyrene, polyester or Mierocrystalline cellulose.

38. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 1, is characterized in that the further stripping of described step (4) electrode comprises and utilize ultrasonic or stir the electrode after making electrolysis and peel off further; Adopt centrifugal method to realize solid-liquid separation, obtain not sufficiently delaminated raw ore and rough Graphene; If use aqueous electrolyte, wetting ability glyoxaline ion liquid electrolytic solution, wetting ability pyridine ionic liquid electrolytic solution or wetting ability pyrrole ionic liquid electrolytic solution electrolysis electrode, then peeling off further the solvent used is water or the aqueous solution containing tensio-active agent, solid water or containing the concentration in the aqueous solution of tensio-active agent between 0.01 mg/ml to 20 mg/ml; If use the electrolytic solution electrolysis electrode containing cyclic carbonate or linear carbonate, then peeling off the solvent used further is organic solvent, and solid concentration is in organic solvent between 0.01 mg/ml to 20 mg/ml.

39. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 38, is characterized in that described tensio-active agent is including but not limited to the one in polyvinylpyrrolidone, polyoxyethylene laurel ether, tween 80, triton X-100, Pluronic P123, Pluronic F127, Pluronic F68, Sodium dodecylbenzene sulfonate, Trimethyllaurylammonium bromide, sodium lauryl sulphate, stearic acid, oleic acid, lauric acid, cetyl trimethylammonium bromide, Tetrabutyl amonium bromide, 4 bromide.

40. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 38, is characterized in that the concentration of described water phase surfactant mixture is between 0.0001 mol/L to 0.5 mol/L.

41. a kind of method being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 38, it is characterized in that described organic solvent is including but not limited to use ethanol, Virahol, acetone, chloroform, tetracol phenixin, tetrahydrofuran (THF), santochlor, N, one in dinethylformamide, N,N-dimethylacetamide, methylformamide, methylacetamide, methyl propanamide, N-Methyl pyrrolidone, N-METHYLFORMAMIDE, methyl-sulphoxide, benzene,toluene,xylene, methylene dichloride, acetonitrile, cyclic carbonate, linear carbonate.

42. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 41, it is characterized in that described cyclic carbonate, linear carbonate is including but not limited to the one in propylene carbonate, methylcarbonate, diethyl carbonate, NSC 11801, Methyl ethyl carbonate.

43. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 38, it is characterized in that described stirring adopts magnetic force or mechanical stirring, the time is 3 hours to 60 hours, whipping temp 20 degrees Celsius to 60 degrees Celsius.

44. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 38, when it is characterized in that described, the frequency of sonic oscillation is that 5 kilohertzs are to 30 kilohertzs, power density 100 watts to 1000 watts, 2 minutes to 10 hours time, temperature 20 degrees Celsius to 60 degrees Celsius; Suspension liquid after ultrasonic under the rotating speed of 500 revs/min to 3000 revs/min centrifugal 5 minutes to 30 minutes.

45. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 1, it is characterized in that the separating-purifying of described step (5) Graphene is including but not limited to four steps: (1) by rough graphene dispersion in a solvent, adopts ultrasonic or stirs and realize being separated of Graphene and solid impurity; (2) by the surperficial solid phase impurity of solid alkaline aqueous solution washing removing obtained for step (1); (3) by the acidic aqueous solution washing neutralization of the solid product after alkali cleaning, and hydrogen ion is utilized to replace other remaining non-carbon ion further; (4) by the solid matter with deionized water after alkali cleaning, pickling or pure water, then adopt centrifugal, suction filtration or filter-pressing method to realize solid-liquid separation, the further drying of gained solid obtains graphene powder.

46. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 45, it is characterized in that described with carbonaceous gauge, Graphene controls between 0.01 mg/ml to 300 mg/ml the concentration of solid in liquid state in step (1), (2), (3) and (4).

47. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 45, it is characterized in that the organic solvent of described separating-purifying is including but not limited to use tetrahydrofuran (THF), tetramethyl-urea, methane amide, N-METHYLFORMAMIDE, N, dinethylformamide, ethanamide, N-methylacetamide, N, N-N,N-DIMETHYLACETAMIDE, N-methyl propanamide, 2-Pyrrolidone, N-Methyl pyrrolidone, pyrroles, pyridine, the one in 2-picoline, 3-picoline, 4-picoline.

48. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 45, it is characterized in that described stirring adopts magnetic force or mechanical stirring, the time is 3 hours to 60 hours, whipping temp 20 degrees Celsius to 60 degrees Celsius.

49. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 45, it is characterized in that the frequency of described sonic oscillation is that 5 kilohertzs are to 30 kilohertzs, power density 100 watts to 1000 watts, 2 minutes to 10 hours time, temperature 20 degrees Celsius to 60 degrees Celsius; Suspension liquid after ultrasonic under 1000 revs/min to 10000 revs/min rotating speeds centrifugal 5 minutes to 30 minutes.

50. a kind of methods being prepared Graphene by graphite raw ore electrolytic process according to claim 45, it is characterized in that in described centrifugal, suction filtration or press filtration including but not limited to using mean pore size the porous polymer bag of (0.2-20 μm) or film between 0.2 micron to 20 microns, solid is stayed in bag, and liquid is thrown out of, extrude, extrude or flow out.

51. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 50, is characterized in that porous polymer bag or film are polypropylene, polyethylene, polystyrene, polyester or Mierocrystalline cellulose are made bag or film.

52. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 45, is characterized in that described alkaline aqueous solution is NaOH or NH ₃h ₂the aqueous solution of O, acidic aqueous solution is the HCl aqueous solution.

53. a kind of methods being prepared Graphene by graphite raw ore electrolytic process as claimed in claim 45, it is characterized in that described drying adopts-50 degrees Celsius of lyophilizes, time of drying is 10 hours to 96 hours, obtains the graphene powder presenting metallic color; Adopt air blast or vacuum-drying, temperature is 70 degrees Celsius to 120 degrees Celsius, and time of drying is 2 hours to 96 hours, obtains the graphene powder presenting metallic color.