CN102868006A - Method for preparing graphene through waste lithium batteries - Google Patents
Method for preparing graphene through waste lithium batteries Download PDFInfo
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- CN102868006A CN102868006A CN2012103582823A CN201210358282A CN102868006A CN 102868006 A CN102868006 A CN 102868006A CN 2012103582823 A CN2012103582823 A CN 2012103582823A CN 201210358282 A CN201210358282 A CN 201210358282A CN 102868006 A CN102868006 A CN 102868006A
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to a method for preparing graphene through waste lithium batteries. The method is characterized in that graphite intercalation compounds in the waste lithium batteries are used as raw materials and stripped to obtain graphene. The method has the advantages that the raw materials are extensive, low in cost and suitable for industrial production, and recycling of resources in the waste lithium batteries is realized while the effective method for preparing graphene is found.
Description
[technical field]
The present invention relates to processing method and the Graphene technical field of waste lithium cell, specifically, the present invention relates to a kind of method for preparing Graphene by waste lithium cell.
[background technology]
Graphene (Graphene) is a kind ofly after fullerene, carbon nano-tube recently to be the allotrope of the human carbon of being familiar with, be a kind of by carbon atom with sp
2Hybridized orbit Cheng Jian, the material with carbon element of the bi-dimensional cellular shape lattice structure of tightly packed formation.Its unique structure has been given the Graphene high-specific surface area, the character that excellent electric property, optical property and mechanical performance etc. attract people's attention is so that Graphene all is with a wide range of applications in a plurality of fields such as molecule sensor, composite material, photoelectric material, stored energies.Therefore the preparation of Graphene and property research thereof have become the focus in the in recent years nano science research.
The preparation method of Graphene is summed up, and mainly contains micromechanics stripping method, chemical vapour deposition technique (CVD), reduction-oxidation graphite method etc.Wherein, the micromechanics stripping method is successfully to prepare the earliest the method for Graphene.The method is that the repeatedly tear-off of utilizing adhesive tape is separated graphene film (K.S.Novoselov, et al.Science, 306,666 (2004)) from highly oriented pyrolytic graphite; Chemical vapour deposition technique is under pyrocarbon hydrogen compound (such as methane) atmosphere, thereby carbon in the hydrocarbon is deposited to make Graphene (Jessica Campos-Delgado on the transition metal substrate, et al.Nano Letters, 8,9 (2008)); Reduction-oxidation graphite method is the main method that prepare in a large number at present Graphenes.Then the method obtains graphene oxide by peeling off first with graphite oxidation, at last the graphene oxide that obtains is obtained Graphene by reduction.Although said method can both successfully make Graphene, but still exist the preparation method complicated, the problems such as cost costliness have restricted a large amount of productions of Graphene.
On the other hand, lithium ion battery has been widely applied to the various fields such as mobile phone, notebook computer, video camera, digital camera since 20th century, succeeded in developing the nineties.In recent years, the annual discarded lithium ion battery in the whole world is in (M.Contestabile, et al.Journal of Power Sources, 92,65 (2001)) more than 1,000,000,000.If do not recycle, not only can cause the serious waste of resource, also pollute the environment.At present, the recovery research of waste lithium cell mainly concentrates on heavy metal ions (such as cobalt, copper, nickel etc.), and few people pay close attention to the wherein recycling problem of graphite resource, graphite and compound between graphite layers in the waste lithium cell directly have been dropped mostly, and this also is a kind of wasting of resources.
For the problems referred to above, the present invention proposes a kind of method for preparing Graphene by waste lithium cell in conjunction with the operation principle of lithium ion battery, has both avoided the waste of graphite resource in the waste lithium cell, also provides a new approach for the preparation Graphene.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, a kind of method for preparing Graphene by waste lithium cell is provided.
The objective of the invention is to be achieved through the following technical solutions:
A kind of preparation method of Graphene, the compound between graphite layers on the waste lithium cell graphite electrode is as raw material, then peels off described compound between graphite layers and makes Graphene.
Described lithium battery specifically is divided into two kinds, and a kind of is lithium metal battery, and a kind of is lithium ion battery.Wherein said lithium metal battery is that metal lithium sheet is negative pole take graphite as anodal, the battery that adding electrolyte, barrier film make; Wherein said lithium ion battery is with agent structure in the charging process not or rare variation, and the lithiated intercalation compound that does not react with electrolyte is for anodal, and graphite is negative pole, adds the battery that electrolyte, barrier film make.
Described waste lithium cell refers to use and discarded lithium battery, for the situation that has contained lithium-compound between graphite layers in the waste lithium cell, directly take out lithium-compound between graphite layers wherein, also can continue lithium-compound between graphite layers that the embedding lithium obtains required exponent number; For the situation that does not contain lithium-compound between graphite layers in the waste lithium cell, can carry out first to graphite wherein the operation of embedding lithium, make lithium-compound between graphite layers, take out again and use.Specifically, be that the operation of embedding lithium is carried out discharge operation to it for lithium metal battery, operation is that it is carried out charging operations for lithium ion battery embedding lithium.
The described method of peeling off compound between graphite layers is selected from a kind of, two or more the combination in the following method: mechanical stripping, remover are peeled off, electrolysis stripping.
Described mechanical stripping makes its bending, depression for compound between graphite layers used, the power of swiping, being pressed into or fracture, thus separate the method for Graphene.The example of mechanical stripping can be to utilize repeatedly tear-off compound between graphite layers of adhesive tape, makes its attenuation, thereby obtains Graphene.Also can be the compound between graphite layers that utilizes the tipless cantilever scraping of atomic force microscope (AFM) to be fixed wtih, obtain the thin slice that scrapes and continue abovementioned steps, finally obtain Graphene.Also can be to utilize ball mill that the compound between graphite layers powder that is scattered in the organic solvent is carried out ball milling, thereby obtain Graphene.Use mechanical stripping can be on the gained Graphene introducing hetero-atoms, but gained Graphene out-of-shape, and preparation process is consuming time longer.
It is electrolyte that described electrolysis stripping inserts metal melting salt, form chemical system take graphite as electrode, compound between graphite layers makes Graphene as anode thereby by the control of regulating current potential, electric weight the metal continuation insertion compound between graphite layers interlayer of electrolysis generation is peeled off.Use electrolysis stripping can prepare on a large scale Graphene, but can leave impurity, for example slaine on the gained Graphene.And whole course of reaction needs higher temperature, reaction environment is required comparatively harsh.
Described remover is peeled off and can be utilized two kinds of removers to peel off: the one, utilize can with the remover of compound between graphite layers reaction, the gas or the bulking effect that discharge by reaction further enlarge the graphite layers distance, make graphite flake layer mutually away from obtaining Graphene to breaking away from the to each other constraint of Van der Waals force, finally peeling off; The 2nd, adopt the surface energy remover close with graphite, because can reduce the entropy of mixing of remover and graphite in the close situation of surface energy, be similar to " similar mixing " principle, so just can allow remover be inserted in the compound between graphite layers, continuing increases the graphite layers distance, obtains Graphene thereby peel off compound between graphite layers.The surface tension of selected remover needs at 10-70mJ/m
2, more preferably at 20-50mJ/m
2Scope in; Above-mentioned surface tension numerical value all is at 20 ℃ of lower sessile drop method test gained.Use the remover strip operation simple, the remover wide material sources mostly are greatly the chemical reagent that often has, can be on prepared Graphene introducing hetero-atoms.
Stripping means most preferably remover is peeled off.
Described remover be selected from inorganic liquid and the organic liquid a kind of, two or more.
Described inorganic liquid is selected from water, inorganic acid aqueous solution, aqueous surfactant solution.
The aqueous solution that described inorganic aqueous acid example is hydrogen chloride, dilute sulfuric acid, rare nitric acid etc.
Described surfactant example is Myrj 45 (Brij 76); softex kw (CTAB); TTAB (TTAB); 1-pyridine acid (PBA); lauryl sodium sulfate (SDS); neopelex (SDBS); lithium dodecyl sulfate (LDS); sodium taurocholate (SC); NaTDC (DOC); cow-bezoar NaTDC (TDOC); 3-[3-(courage amido propyl) dimethylamino] the interior sodium (CHAPS) of propane sulfonic acid; kayexalate (PSS); polyvinylpyrrolidone (PVP); dodecyl-β-D-Maltose glycosides (DBDM); nonoxinol (IGEPAL CO-890); octadecanoic acid ester of polyethylene glycol (Tween 80) etc.
Described organic liquid is selected from alcohol, ketone, ester, amine, sulfone, chlorobenzene, organic acid, ionic liquid.
Wherein said alcohol is the alcohol that contains 1-6 carbon atom.Example can be methyl alcohol, ethanol, ethylene glycol, 1-propyl alcohol, 2-propyl alcohol, 1,2-PD, 1,3-PD, glycerol, n-butyl alcohol, 1-amylalcohol, 1-hexanol etc.;
Wherein said acid is the acid that contains 1-6 carbon atom.Example can be formic acid, acetic acid, ethanedioic acid, 1-propionic acid, 2-propionic acid, 1,2-malonic acid, 1,3-malonic acid, the third three acid, 1-butyric acid, 1-valeric acid, 1-caproic acid etc.;
The example of wherein said ketone can be acetone, 1-Methyl-2-Pyrrolidone, NVP, octylpyrrolidone, dodecyl pyrrolidone, DMI etc.;
The example of wherein said ester can be gamma-butyrolacton, Ergol etc.;
The example of wherein said amine can be dimethyl formamide, DMA, DMF etc.;
The example of wherein said sulfone can be dimethyl sulfoxide (DMSO) etc.;
The example of wherein said chlorobenzene can be o-dichlorohenzene etc.;
The example of wherein said ionic liquid can be [Bmim] [BF
4], [Bmim] [Tf
2N], [C
4Mim] [PF
6], [C
8Mim] [PF
6], [C
4Mim] Cl, [C
8Mim] Cl etc.
Also can be selected from the mixture of aforesaid two or more composition of liquid, as: water/methyl alcohol, water/ethanol, water/formic acid, ethanol/acetic acid, water/ethanol/acetic acid, 1-METHYLPYRROLIDONE/water, [Bmim] [BF
4]/water, [C4mim] [PF
6]/dimethyl formamide etc.
The productive rate of Graphene is quality and the raw material graphite mass ratio of obtained Graphene.The quality of the Graphene directly final solid graphite alkene of weighing obtains, and also can derive from the concentration of Graphene in the graphene dispersing solution.In the graphene dispersing solution concentration of Graphene be utilize the absorbance measure graphene dispersing solution (tester as: 722N visible spectrophotometer (Shanghai Precision Scientific Apparatus Co., Ltd's manufacturing)), follow that Lambert-Beer's law calculates.
The structural information of compound between graphite layers can utilize X ray diffracting spectrum (XRD) to measure that (tester is such as: D/MAX 2550 VB/PC (Japanese Rigaku company make), target source: the copper target).
The thickness number of plies of described Graphene and length and width size can utilize atomic force microscope images (AFM) to determine (tester as: NanoScopeIIIaMultiMode AFM (manufacturing of U.S. Veeco company), operator scheme: rap pattern).
The length and width size of described Graphene and the number of plies also can be determined with transmission electron microscope (TEM) and the electronic diffraction that carries thereof (tester is such as: TEM (JEM-2100) (Japanese JEOL company make)).
The defect level of Graphene can utilize the strength ratio (I at D peak and G peak among Raman spectrum (Raman) figure
D/ I
G) value determines I
D/ I
GBe worth greatlyr, Graphene contained defective is more, and (tester is such as inVia+Reflex (manufacturing of Britain Renishaw company), laser wavelength: 514nm).
Compared with prior art, good effect of the present invention is:
(1) raw material of this method is a large amount of waste lithium cell, and the source is abundant;
(2) this method has successfully been recycled the graphite resource in the waste lithium cell, avoids waste, and turns waste into wealth;
(3) it is simple that the present invention prepares the method for Graphene, is fit to suitability for industrialized production.
[description of drawings]
Fig. 1 makes the lithium-compound between graphite layers of single order and X-ray diffraction (XRD) figure of raw material graphite according to embodiment 1, and wherein a refers to compound between graphite layers, and b refers to graphite.
Fig. 2 is that Graphene according to embodiment 1 preparation is at SiO
2Atomic force microscope on the/Si substrate (AFM) Fig. 5 .00 * 5.00 μ m sizes (a), 1.95 * 1.95 μ m sizes (b) and altitude profile figure (c).
Fig. 3 is the Raman spectrogram according to the Graphene of embodiment 1 preparation.
Fig. 4 is according to the transmission electron microscope (TEM) of the Graphene of embodiment 3 preparation (a) and constituency (black dotted lines zone) electron diffraction diagram (b).
[embodiment]
The preparation method's of a kind of Graphene of the present invention embodiment below is provided.
Use the waste and old lithium metal battery after discharging
Used waste and old lithium metal battery is as anodal take graphite electrode, metal lithium sheet is as battery cathode, lithium hexafluoro phosphate be dissolved in volume ratio be solution in 1: 1: 1 EC/EMC/DMC (ethylene carbonate/methyl ethyl carbonate/dimethyl carbonate) ternary mixed solvent as electrolyte, barrier film adopts polypropylene porous film.Wherein, graphite electrode is by with special spherical graphite SSG (active material) (deriving from Loudi, Hunan brightness space Science and Technology Ltd.), acetylene black (conductive agent, particle diameter: about 10nm), Kynoar PVDF (binding agent) in mass ratio 8: 1: 1 ratio mix, adding 1-Methyl-2-Pyrrolidone (NMP) makes PVDF concentration in 0.005～0.03g/ml scope, stir the furnishing pasty slurry.Its uniform spreading is overlayed on the Copper Foil, after solvent evaporates is complete, utilize card punch to make.The voltage of this waste and old lithium metal battery is 0.087V.
Discharge mode adopts pulsed discharge, and (tester is such as BTS high accuracy battery detection system (the new Weir Electronics Co., Ltd. of China makes), model: CT-3008W-5V10mA-S1), after arranging according to parameter given below, can carry out pulsed discharge: carried out constant-current discharge 5 minutes with the discharge rate of 0.05C in each circulation, left standstill 12 minutes, successively circulation.Pulse discharge time is 7 days, then stops discharge.Thereby obtain single order lithium-compound between graphite layers.
This waste and old lithium metal battery placed in water, the glove box of oxygen content less than 1ppm disassemble, take out anodal single order lithium-compound between graphite layers.After the electrolyte volatilization, with lithium-compound between graphite layers scrape gently from the Copper Foil from, place in the agate mortar and grind to form uniform powder, in glove box, pour into rapidly the deionized water behind the lithium-compound between graphite layers of taking-up powdery, deionized water described herein is as remover, the lithium metal in lithium-compound between graphite layers is peeled off and made Graphene.
Utilize spectrophotometer to record the concentration of gained Graphene aqueous dispersions, thus the output of the Graphene that obtains making, and then obtain productive rate.Adopting the Graphene productive rate of preceding method gained the present embodiment is 0.59%.
Fig. 1 is the XRD figure of the lithium-compound between graphite layers in the waste and old inner metal battery and graphite SSG after the discharge among the embodiment 1.Can find out: an obvious spike has appearred in lithium-compound between graphite layers near 24 °, and near the graphite characteristic peak 26 ° does not occur, and this phenomenon has proved that lithium-compound between graphite layers is 1 rank.
Fig. 2 embodiment 1 makes the AFM figure of Graphene, and the Graphene height that figure (c) is corresponding is 0.8nm, is individual layer.Graphene thickness is between 0.8～7.3, and the number of plies is approximately between 1～21 layer.Length and width are all between 100nm～5000nm.
Fig. 3 has provided the Raman spectrogram (abscissa is wave number, and ordinate is intensity) of the Graphene of embodiment 1 preparation, can find out the existence of graphite-structure in the G peak explanation Graphene, the existence of defective in the D peak explanation Graphene.The strength ratio I at D peak and G peak
D/ I
GValue is 0.68.
Directly use waste and old lithium metal battery
Except old and useless battery not being discharged, all the other operations are identical with embodiment 1, final gained Graphene productive rate is 0.51%, gained Graphene thickness is between 2.4～9.2, be that the number of plies is approximately between 6～26 layers, length and width all between 120～6300nm, the strength ratio I at D peak and G peak in the Raman spectrum
D/ I
GValue is 0.68.
Embodiment 3
Use the waste and old lithium ion battery after charging
Used waste lithium ion cell anode active material is cobalt acid lithium, and negative active core-shell material is native graphite 918.This waste and old lithium ion battery voltage is 3.7V.Charging operations is specially battery to carry out constant current charge to cell voltage with the charge rate of 0.2C and rises to 4.2V.Carry out afterwards constant voltage charge to charge rate and be down to 0.02C, after shelving 30min, again battery is carried out constant current charge with the charge rate of 0.2C and be charged to first 4.35V, constant voltage charge to charge rate is down to 0.02C (tester is such as: BTS high accuracy battery detection system (the new Weir Electronics Co., Ltd. of China makes), model: CT-3008W-5V10mA-S1) again.
Then stop charging, in water, the glove box of oxygen content less than 1ppm, disassemble battery, take out the single order lithium-compound between graphite layers of negative pole.After the electrolyte volatilization, with lithium-compound between graphite layers scrape gently from the copper sheet from, place in the agate mortar and grind to form uniform powder, in glove box, pour into rapidly the deionized water behind the lithium-compound between graphite layers of taking-up powdery, deionized water described herein is as remover, the lithium metal in lithium-compound between graphite layers is peeled off and made Graphene.Final gained Graphene productive rate is 0.63%, and gained Graphene thickness is between 0.8～12.6, and namely the number of plies is approximately between 1～37 layer, length and width all between 100～15000nm, the strength ratio I at D peak and G peak in the Raman spectrum
D/ I
GValue is 0.73.
Figure 4 shows that the TEM figure of wherein a slice Graphene that embodiment 3 makes.Can be found out by this TEM figure, being about of gained Graphene is 2000nm, is wider than 1000nm.Can find out from electron diffraction diagram, the brightness of internal layer hot spot is better than outer hot spot, and namely the diffracted intensity of (0110) face of Graphene is better than (1210) face, has proved that the Graphene among Fig. 4 (a) is individual layer
Embodiment 4
Directly use waste and old lithium ion battery.
Except waste and old lithium ion battery not being charged, other operate with embodiment 3.Final gained Graphene productive rate is 0.58%, and gained Graphene thickness is between 1.4～12nm, and namely the number of plies is approximately between 3～35 layers, length and width all between 300～15000nm, the strength ratio I at D peak and G peak in the Raman spectrum
D/ I
GValue is 0.76.
Embodiment 5
Directly use waste and old lithium ion battery.
Except used anode active material of lithium ion battery is LiFePO4, other operate with embodiment 4.Final gained Graphene productive rate is 0.62%, and gained Graphene thickness is between 1.7～11.7nm, and namely the number of plies is approximately between 4～34 layers, length and width all between 220～15400nm, the strength ratio I at D peak and G peak in the Raman spectrum
D/ I
GValue is 0.74.
Embodiment 6
Directly use waste and old lithium ion battery.
Except used anode active material of lithium ion battery is LiMn2O4, electrolyte is biasfluoroethylene-hexafluoropropylene (VDF-HFP) copolymer, polymethyl methacrylate (PMMA), lithium perchlorate, ethylene carbonate (EC) and the butyrolactone (homogeneous mixture (mass ratio: 21/14/5.4/29.8/29.8) of γ-GBL), waste and old lithium ion battery voltage is outside the 3.7V, and other operate with embodiment 4.Final gained Graphene productive rate is 0.53%, and gained Graphene thickness is at 2.3～12.6nm, and namely the number of plies is approximately between 6～37 layers, length and width all between 210～14300nm, the strength ratio I at D peak and G peak in the Raman spectrum
D/ I
GValue is 0.78.
Embodiment 7
The mechanical stripping method is peeled off lithium-compound between graphite layers and is prepared Graphene
Lithium-compound between graphite layers in the waste and old lithium ion battery after the embodiment 3 described chargings is as raw material, in water, the glove box of oxygen content less than 1ppm, get 0.02g lithium-compound between graphite layers powder and be scattered in the dimethyl benzene acid amides (DMF), stir.Then and zirconia ball (diameter 2.0-2.5mm, heavy 200g) put into together a polytetrafluoroethylene bottle, the polytetrafluoroethylene bottle is sealed.Utilize ball mill (use instrument as: QM-3SP2 planetary ball mill (Nanjing Univ. Instrument Factory)) with the rotating speed ball milling 30h of 300rpm.Take out afterwards the gained dispersion liquid with 4000rpm, carried out centrifugal 30 minutes, finally obtain containing the upper strata dispersion liquid of Graphene.Final gained Graphene productive rate is 0.59%, and gained Graphene thickness is between 0.9～4.9nm, and namely the number of plies is approximately between 1～14 layer, length and width all between 80～8700nm, the strength ratio I at D peak and G peak in the Raman spectrum
D/ I
GValue is 0.78.
Embodiment 8
The electrolysis stripping method is peeled off lithium-compound between graphite layers and is prepared Graphene
Lithium-compound between graphite layers in the waste and old lithium ion battery of electrolysis unit after with embodiment 3 described chargings is as negative electrode, high purity graphite (impurity is less than 35ppm) crucible (high 140mm, internal diameter 20mm, external diameter 30mm) as anode, the melting lithium chloride is as electrolyte.Use one can temperature control vertical heater and be connected with the sealing corundum tubular reactor of water cooling plant.99% pure lithium chloride is adding in the reactor after super-dry, and then the speed with 150ml/min pours into high-purity argon in reactor, is used for the gas of purge reactor, keeps the inert atmosphere of reactor in case the generation of oxidation reaction.After continuing to pass into high-purity argon, begin to heat up, reach 850 ℃ after about 3 hours, behind the sodium fusion to be chlorinated, negative electrode is slowly inserted in the fuse salt.Constant current with 10A carried out electrolysis 3 hours afterwards.After electrolysis finishes, after the device cooling, take out sealed reactor and transfer in water, the glove box of oxygen content less than 1ppm, scrape off sodium chloride residual on the negative electrode, negative electrode is cleaned repeatedly with deionized water obtain Graphene after removing impurity.Final gained Graphene productive rate is 0.62%, and gained Graphene thickness is between 4.8～13nm, and namely the number of plies is approximately between 13～38 layers, length and width all between 72～5400nm, the strength ratio I at D peak and G peak in the Raman spectrum
D/ I
GValue is 0.78.
Embodiment 9～29
The remover stripping method is peeled off lithium-compound between graphite layers and is prepared Graphene
Lithium-compound between graphite layers in the waste and old lithium ion battery after the embodiment 3 described chargings is as raw material, lithium-compound between graphite layers powder is dropped in the remover, (use instrument such as ultrasonic cleaner (Chinese Shanghai section leads ultrasonic instrument Co., Ltd and makes) at ultrasonic wave, model: SK2510LHC) under the 53Hz environment ultrasonic 30 minutes, under the 500rpm rotating speed, (use instrument such as flying pigeon board centrifuge (Chinese Shanghai peace booth scientific instrument factory makes) afterwards, model: TDL80-2B) centrifugal 90 minutes, obtain Graphene.The used remover of the present embodiment is selected from alcohol, ketone, ester, amine, sulfone, chlorobenzene, organic acid, the ionic liquid in inorganic acid aqueous solution, aqueous surfactant solution and the organic liquid in the aforementioned inorganic liquid.NMP:1-N-methyl-2-2-pyrrolidone N-wherein, DMF: dimethyl benzene acid amides.
Embodiment 30～38
The remover stripping method is peeled off lithium-compound between graphite layers and is prepared Graphene.
Lithium-compound between graphite layers in the waste and old lithium ion battery after the embodiment 3 described chargings is as raw material, lithium-compound between graphite layers powder is dropped in the remover, (use instrument such as ultrasonic cleaner (Chinese Shanghai section leads ultrasonic instrument Co., Ltd and makes) at the 53Hz ultrasonic wave, model: SK2510LHC) under the environment ultrasonic 30 minutes, under the 500rpm rotating speed, (use instrument such as flying pigeon board centrifuge (Chinese Shanghai peace booth scientific instrument factory makes) afterwards, model: TDL80-2B) centrifugal 90 minutes, obtain Graphene.The used remover of the present embodiment is selected from two or more the mixture of component of aforementioned inorganic liquid and organic liquid.
Embodiment 39
Remover peels off/and the combination of mechanical stripping method peels off lithium-compound between graphite layers and prepares Graphene
Lithium-compound between graphite layers in the waste and old lithium ion battery after the embodiment 3 described chargings is as raw material, getting lithium-compound between graphite layers powder 0.02g drops in the dimethyl benzene acid amides (DMF), (use instrument such as ultrasonic cleaner (Chinese Shanghai section leads ultrasonic instrument Co., Ltd and makes) at the 53Hz ultrasonic wave, model: SK2510LHC) under the environment ultrasonic 40 minutes, afterwards with this dispersion liquid and zirconia ball (diameter 2.0-2.5mm, heavy 200g) puts into together a polytetrafluoroethylene bottle, the polytetrafluoroethylene bottle is sealed.Utilize ball mill (use instrument as: QM-3SP2 planetary ball mill (Nanjing Univ. Instrument Factory)) with the rotating speed ball milling of 300rpm 25 hours.Take out afterwards the gained dispersion liquid with 4000rpm, carry out centrifugally (using instrument such as flying pigeon board centrifuge (Chinese Shanghai peace booth scientific instrument factory makes), model: TDL80-2B) 30 minutes, finally to obtain containing the upper strata dispersion liquid of Graphene.Final gained Graphene productive rate is 0.72%, and gained Graphene thickness is between 0.8～8.8nm, and namely the number of plies is approximately between 1～25 layer, length and width all between 60～14000nm, the strength ratio I at D peak and G peak in the Raman spectrum
D/ I
GValue is 0.79.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered as in protection scope of the present invention.
Claims (7)
1. a method for preparing Graphene by waste lithium cell is characterized in that, the compound between graphite layers in the waste lithium cell is peeled off described compound between graphite layers and made Graphene as raw material.
2. the preparation method of Graphene as claimed in claim 1 is characterized in that, the described method of peeling off compound between graphite layers is selected from a kind of in the following method, and two or more combination: mechanical stripping, remover are peeled off, electrolysis stripping.
3. the preparation method of Graphene as claimed in claim 2 is characterized in that, the described method of peeling off compound between graphite layers is that remover is peeled off.
4. the preparation method of Graphene as claimed in claim 3 is characterized in that, described remover be selected from inorganic liquid and the organic liquid a kind of, two or more.
5. the preparation method of Graphene as claimed in claim 4 is characterized in that, described inorganic liquid is selected from water, inorganic acid aqueous solution, aqueous surfactant solution.
6. the preparation method of Graphene as claimed in claim 5 is characterized in that, described inorganic liquid is water.
7. the preparation method of Graphene as claimed in claim 4 is characterized in that, described organic liquid is selected from: alcohol, ketone, ester, amine, sulfone, chlorobenzene, organic acid, ionic liquid.
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| CN103259062A (en) * | 2013-04-17 | 2013-08-21 | 清华大学深圳研究生院 | Method for regenerating graphene by recovering waste lithium ion battery |
| CN103633393A (en) * | 2013-12-06 | 2014-03-12 | 河南师范大学 | Recycling process for active material of waste cathode piece of lithium ion battery |
| CN103641107A (en) * | 2013-12-11 | 2014-03-19 | 江苏科技大学 | Method for preparing graphene from waste battery graphite rod |
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