CN103058174A - Preparation method of graphene - Google Patents
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- CN103058174A CN103058174A CN2011103179397A CN201110317939A CN103058174A CN 103058174 A CN103058174 A CN 103058174A CN 2011103179397 A CN2011103179397 A CN 2011103179397A CN 201110317939 A CN201110317939 A CN 201110317939A CN 103058174 A CN103058174 A CN 103058174A
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Abstract
The invention relates to a preparation method of graphene, which is a new method for preparing graphene by using an electrochemistry technology, and is characterized in that a graphite rod is taken as positive and negative electrodes of a work electrode, an electrolyte solution of lithium ions can be taken as an electrolyte, under the effect for applying the voltage, the charge and discharge operation can be carried out, the graphite electrode is stripped to a thin graphite slice containing lithium ion and is dispersed in the electrolyte, the electrolyte is performed with an ultrasonic treatment, and is filtered and washed to obtain a graphene solution or a graphene solid. By using the electrochemistry method, the new preparation method for graphene with low cost, high efficiency and large output can be provided, and the graphene can be used for various fields such as power supply materials, composite materials, sensors and transistors.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene, the method is a kind of novel method of utilizing electrochemical techniques to prepare Graphene.
Background technology
Graphene is the bi-dimensional cellular shape structure by the tightly packed one-tenth of carbon atom, is a kind of novel Two-dimensional Carbon nano material, is present the thinnest material in the world.The crystalline structure that Graphene is complete, guaranteed electronics straightway migration on the Graphene plane, its rate of migration is the tens of to hundreds of times of conventional semiconductor material, make Graphene possess good electroconductibility, and probably replace silicon and become the transistorized base mateiral of ultra high frequency of future generation and be widely used in high performance integrated circuit and the novel nano electron device.Graphene also has the intensity of superelevation, between carbon atom powerful reactive force make it become the at present known the highest material of mechanical strength, and might be applied in the novel matrix material.The electroconductibility that Graphene the is good and high-permeability of light made its unique advantage in the application of transparent conductive film, and this class film is most important in fields such as liquid-crystal display and solar cells.Specific surface area is large, electric property is excellent, the carrier mobility advantages of higher because Graphene has, and therefore has a good application prospect in a plurality of fields such as power material, matrix material, sensor, transistors.
Graphene makes by the micromechanics stripping method the earliest.2004, the Geim of University of Manchester etc. peeled a small amount of single-layer graphene film with adhesive tape from graphite, becomes the discoverer of Graphene, although this method can obtain quality preferably individual layer and double-layer graphite alkene, output and efficient are all too low.
In recent years, people constantly explore novel method to improve the output of Graphene, and wherein oxidation reduction process is owing to its stability is widely adopted.This method at first prepares graphite oxide, first Graphite Powder 99 is dispersed in the strong oxidizing property mixing acid, for example then concentrated nitric acid and the vitriol oil add potassium permanganate or Potcrate and wait by force oxygenant to obtain graphite oxide, obtain graphene oxide through supersound process again, obtain Graphene by reduction at last.Yet oxidising process can cause a large amount of textural defect, even these defectives can not be eliminated fully through 1100 ℃ of annealing, still has the residual of many hydroxyls, epoxy group(ing), carbonyl, carboxyl.The electronic structure that defective causes changes makes Graphene transfer semi-conductor to by conductor, has a strong impact on the electric property of Graphene, has restricted its application.But the existence of oxy radical makes Graphene be easy to be dispersed in the solvent, and makes graphene functionalized, is easy to and a lot of substance reaction, makes graphene oxide become the basis of preparation Graphene functional composite material.
Lotya etc. obtain stable graphene suspension, but there is the problem of inefficiency in the method by the ultrasonic graphite of peeling off in water-tensio-active agent.The people such as Kian Ping Loh utilize the method for lithium ion battery fast charging and discharging, after in the organic electrolyte of Li, discharging and recharging for some time, realized the preparation of Graphene with high-power ultrasonic, but in this technology ultrasonic and organic solvent are had relatively high expectations, and the Graphene number of plies of producing is more, can't really realize the preparation of Graphene, the Graphene surface imperfection of this method preparation is more in addition, is unfavorable for practical application.In addition, domestic with Shenyang metal institute, what the units such as CAS Institute of Physics realized utilizes the technology of vapor phase deposition to realize the growth of Graphene in Ni-based ground, realized breakthrough progress in the Graphene field, but this technology has no idea to realize large batch of preparation at present, exists certain difficulty in Application Areas.
Summary of the invention
The novel preparation method that the purpose of this invention is to provide a kind of Graphene.
The present invention adopts electrochemical method, has proposed the novel preparation method of a kind of low cost, efficient high, Graphene that output is large, can be used for a plurality of fields such as power material, matrix material, sensor, transistor with the Graphene of the method preparation.
Technical scheme of the present invention is:
With graphite rod as working electrode, with the electrolyte solution of lithium ion as ionogen, apply voltage-10～10 volt, discharge and recharge operation, in the process that discharges and recharges, make the insertion and the release that circulate in the carbon-coating of lithium ion in electrode, so that carbon-coating becomes is more and more loose, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution.Electrolytic solution is carried out supersound process make the graphite flake of peeling off become Graphene, can obtain the good Graphene of dispersity.Through the solution or the Graphene solid that filter, washing can obtain Graphene.The method is easy and simple to handle, and efficient is good, and the Graphene properties of preparation is excellent, be a kind of low cost, fast, the novel preparation method of the Graphene of environmental protection.
Graphite rod is as the positive and negative electrode of working electrode, under the effect of electric current, lithium ion can be inserted in the carbon molecular layer of Graphite Electrodes, make the graphite carbon-coating become more and more loose, at last from the carbon-point sur-face peeling, the graphite layers of peeling off is large apart from continue change in the process that discharges and recharges, thereby forms Graphene.Positive and negative electrode all adopts Graphite Electrodes as working electrode, and Graphene can be produced from positive and negative two electrodes, and positive and negative electrode all can be produced Graphene like this, increase Graphene output that can be at double.
Applying voltage all can prepare Graphene under-10～10 volts in present method between the electrode, the increase of voltage can increase the preparation speed of Graphene, but too highly also can bring side reaction, increases the generation of hydrogen and oxygen.The voltage that applies between present method is selected-10～10 volts through many experiments prepares Graphene, preferred-8～8 volts voltage.
In electrolytic reaction, electrolytic solution in the electrolyzer is carried out supersound process, can accelerate the speed that Graphene is peeled off from Graphite Electrodes, simultaneously Graphene is more evenly distributed in electrolytic solution, can prevent and reduce the reunion of Graphene, improve the quality of Graphene product.It is to carry out synchronously with electrolytic reaction that the present invention adopts supersound process, is that electrolytic reaction and supersound process are integrated, makes the more succinct and optimization of production technique.
The present invention also can adopt supersound process and electrolytic reaction step-by-step processing, carries out first electrolytic reaction, makes graphite flake peel off out, then in next step solution that contains graphite flake is carried out supersound process, obtains the good Graphene of dispersity.
The electrolyte solution that the present invention adopts lithium ion in the selection of electrolytic solution is as ionogen, and the electrolyte solution of described lithium ion refers to the solution of lithium halide or lithium perchlorate or the mixing solutions of the two.Lithium halide refers to lithium chloride, lithiumbromide and lithium iodide.The preferred lithium chloride of wherein said lithium halide.Wherein said lithium halide can refer to lithiumbromide.Wherein said lithium halide can refer to lithium iodide.When electrolytic solution was the mixing solutions of lithium halide or lithium perchlorate, the mol ratio of lithium halide and lithium perchlorate was 1: 9～9: 1, and the mol ratio of preferred lithium halide and lithium perchlorate is 4: 6～6: 4.
The electrolyte solution of lithium ion of the present invention also is the aqueous solution of lithium ion, also can be the organic solution of lithium ion, also can be the mixing solutions of water and organic solvent.The organic solvent that organic solution is selected refers to dimethyl carbonate, ethanol, ethylene glycol, propylene glycol, butyleneglycol, trichloromethane, methylene dichloride, acetonitrile etc.
To solution or the Graphene solid that the Graphene that strips down filters, washing can obtain Graphene.
Description of drawings:
Fig. 1 is electrolyzer and Graphite Electrodes work synoptic diagram.
Fig. 2: be the atomic force microscope picture of Graphene of preparation.
Fig. 3 is the surperficial Raman signal of the Graphene of experiment preparation.
Fig. 4 is the sign that the physical properties general measuring instrument carries out the Graphene for preparing.
Embodiment:
In typical electrochemical workstation as shown in Figure 1, with the positive and negative electrode of graphite rod as working electrode, with the electrolyte solution of lithium ion as ionogen, applying under the voltage effect, discharge and recharge operation, make the insertion and the release that circulate in the carbon-coating of lithium ion in electrode, so that carbon-coating becomes is more and more loose, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution, simultaneously electrolytic solution is carried out supersound process and make the graphite flake of peeling off become Graphene, can obtain the good Graphene of dispersity.Also can carry out to the electrolytic solution of graphitiferous thin slice supersound process and be placed on electrolytic reaction and carry out after finishing, obtain the good Graphene of dispersity.To solution or the Graphene solid that the Graphene that strips down filters, washing can obtain Graphene.Resulting Graphene is carried out analysis and characterization, and characterization result is seen accompanying drawing 2, accompanying drawing 3, accompanying drawing 4.The Graphene that observes the present invention preparation from accompanying drawing 2 can obtain the Graphene thin layer greater than the larger area size of 3 microns of 3 microns *.Can observe the Graphene that the Graphene of the present invention preparation has the different numbers of plies from accompanying drawing 3, the carbon-coating number of Graphene mainly concentrates on the 3-4 layer.The Graphene that can observe the present invention preparation from accompanying drawing 4 has been different from the low-temperature performance of original graphite fully, has shown at low temperatures the performance of spin glass attitude, has proved that the method prepares the reliability of Graphene.
Following embodiment will further specify the present invention.
Embodiment 1
In the work system of a typical electrochemical workstation, provide energy derive by electrochemical workstation or other power supplys, with the positive and negative electrode of graphite rod as working electrode, take the aqueous solution of lithium chloride as ionogen, the concentration of lithium ion is 3mol/L, discharges and recharges operation, applies voltage to be-the 10-10 volt, discharge and recharge operation, carry out ultrasonic to electrolytic solution in the electrolyzer simultaneously.In the process that discharges and recharges, make the insertion and the release that circulate in the carbon-coating of lithium ion in electrode, so that carbon-coating becomes is more and more loose, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution.The graphite layers peeled off is apart from becoming large in the process that discharges and recharges, then these graphite flakes of peeling off are carried out ultrasonicly, can obtain the good Graphene of dispersity.To solution or the Graphene solid that the Graphene that strips down filters, washing can obtain Graphene.
Embodiment 2
In the work system of a typical electrochemical workstation, provide energy derive by electrochemical workstation or other power supplys, with the positive and negative electrode of graphite rod as working electrode, take the aqueous solution of lithiumbromide as ionogen, the concentration of lithium ion is 2mol/L, discharges and recharges operation, applies voltage to be-the 8-8 volt, discharge and recharge operation, carry out ultrasonic to electrolytic solution in the electrolyzer simultaneously.In the process that discharges and recharges, make the insertion and the release that circulate in the carbon-coating of lithium ion in electrode, so that carbon-coating becomes is more and more loose, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution.The graphite layers peeled off is apart from becoming large in the process that discharges and recharges, then these graphite flakes of peeling off are carried out ultrasonicly, can obtain the good Graphene of dispersity.To solution or the Graphene solid that the Graphene that strips down filters, washing can obtain Graphene.
Embodiment 3
In the work system of a typical electrochemical workstation, provide energy derive by electrochemical workstation or other power supplys, with the positive and negative electrode of graphite rod as working electrode, take the aqueous solution of lithium iodide as ionogen, the concentration of lithium ion is 1mol/L, discharge and recharge operation, applying voltage is-the 6-6 volt to discharge and recharge operation.In the process that discharges and recharges, make the insertion and the release that circulate in the carbon-coating of lithium ion in electrode, so that carbon-coating becomes is more and more loose, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution.Then the graphite layers of peeling off carries out supersound process to the electrolytic solution that contains these graphite flakes of peeling off apart from become large in the process that discharges and recharges, and can obtain the good Graphene of dispersity.To solution or the Graphene solid that the Graphene that strips down filters, washing can obtain Graphene.
Embodiment 4
In the work system of a typical electrochemical workstation, provide energy derive by electrochemical workstation or other power supplys, with the positive and negative electrode of graphite rod as working electrode, take the aqueous solution of lithium perchlorate as ionogen, the concentration of lithium ion is 0.5mol/L, discharges and recharges operation, applies voltage to be-the 5-5 volt, discharge and recharge operation, carry out ultrasonic to electrolytic solution in the electrolyzer simultaneously.In the process that discharges and recharges, make the insertion and the release that circulate in the carbon-coating of lithium ion in electrode, so that carbon-coating becomes is more and more loose, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution.The graphite layers peeled off is apart from becoming large in the process that discharges and recharges, then these graphite flakes of peeling off are carried out ultrasonicly, can obtain the good Graphene of dispersity.To solution or the Graphene solid that the Graphene that strips down filters, washing can obtain Graphene.
Embodiment 5
In the work system of a typical electrochemical workstation, provide energy derive by electrochemical workstation or other power supplys, with the positive and negative electrode of graphite rod as working electrode, take the ethanolic soln of lithium perchlorate as ionogen, the concentration of lithium ion is 0.1mol/L, discharges and recharges operation, applies voltage to be-the 4-4 volt, discharge and recharge operation, carry out ultrasonic to electrolytic solution in the electrolyzer simultaneously.In the process that discharges and recharges, make the insertion and the release that circulate in the carbon-coating of lithium ion in electrode, so that carbon-coating becomes is more and more loose, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution.The graphite layers peeled off is apart from becoming large in the process that discharges and recharges, then these graphite flakes of peeling off are carried out ultrasonicly, can obtain the good Graphene of dispersity.To solution or the Graphene solid that the Graphene that strips down filters, washing can obtain Graphene.
Embodiment 6
In the work system of a typical electrochemical workstation, provide energy derive by electrochemical workstation or other power supplys, with the positive and negative electrode of graphite rod as working electrode, take the ethanolic soln of lithium chloride and lithium perchlorate as ionogen, the concentration of lithium ion is 1mol/L, and the mol ratio of lithium chloride and lithium perchlorate is 5: 5, discharge and recharge operation, applying voltage is-the 4-4 volt, discharges and recharges operation, carries out ultrasonic to electrolytic solution in the electrolyzer simultaneously.In the process that discharges and recharges, make the insertion and the release that circulate in the carbon-coating of lithium ion in electrode, so that carbon-coating becomes is more and more loose, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution.The graphite layers peeled off is apart from becoming large in the process that discharges and recharges, then these graphite flakes of peeling off are carried out ultrasonicly, can obtain the good Graphene of dispersity.To solution or the Graphene solid that the Graphene that strips down filters, washing can obtain Graphene.
Embodiment 7
In the work system of a typical electrochemical workstation, provide energy derive by electrochemical workstation or other power supplys, with the positive and negative electrode of graphite rod as working electrode, take the ethanolic soln of lithium chloride, lithiumbromide and lithium perchlorate as ionogen, the concentration of lithium ion is 1mol/L, and the mol ratio of lithium chloride, lithiumbromide and lithium perchlorate is 2: 2: 6, discharge and recharge operation, applying voltage is-the 3-3 volt, discharges and recharges operation, carries out ultrasonic to electrolytic solution in the electrolyzer simultaneously.In the process that discharges and recharges, make the insertion and the release that circulate in the carbon-coating of lithium ion in electrode, so that carbon-coating becomes is more and more loose, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution.The graphite layers peeled off is apart from becoming large in the process that discharges and recharges, then these graphite flakes of peeling off are carried out ultrasonicly, can obtain the good Graphene of dispersity.To solution or the Graphene solid that the Graphene that strips down filters, washing can obtain Graphene.
Embodiment 8
In the work system of a typical electrochemical workstation, provide energy derive by electrochemical workstation or other power supplys, with the positive and negative electrode of graphite rod as working electrode, take the ethylene glycol solution of lithium iodide and lithium perchlorate as ionogen, the concentration of lithium ion is 1.6mol/L, and the mol ratio of lithium iodide and lithium perchlorate is 6: 4, discharge and recharge operation, applying voltage is-the 5.5-5.5 volt, discharges and recharges operation, carries out ultrasonic to electrolytic solution in the electrolyzer simultaneously.In the process that discharges and recharges, make the insertion and the release that circulate in the carbon-coating of lithium ion in electrode, so that carbon-coating becomes is more and more loose, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution.The graphite layers peeled off is apart from becoming large in the process that discharges and recharges, then these graphite flakes of peeling off are carried out ultrasonicly, can obtain the good Graphene of dispersity.To solution or the Graphene solid that the Graphene that strips down filters, washing can obtain Graphene.
Embodiment 9
In the work system of a typical electrochemical workstation, provide energy derive by electrochemical workstation or other power supplys, with the positive and negative electrode of graphite rod as working electrode, take the dimethyl carbonate solution of lithiumbromide and lithium perchlorate as ionogen, the concentration of lithium ion is 1.6mol/L, and the mol ratio of lithiumbromide and lithium perchlorate is 9: 1, discharge and recharge operation, applying voltage is-the 3-3 volt, discharges and recharges operation, carries out ultrasonic to electrolytic solution in the electrolyzer simultaneously.In the process that discharges and recharges, make the insertion and the release that circulate in the carbon-coating of lithium ion in electrode, so that carbon-coating becomes is more and more loose, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution.The graphite layers peeled off is apart from becoming large in the process that discharges and recharges, then these graphite flakes of peeling off are carried out ultrasonicly, can obtain the good Graphene of dispersity.To solution or the Graphene solid that the Graphene that strips down filters, washing can obtain Graphene.
Embodiment 10
In the work system of a typical electrochemical workstation, provide energy derive by electrochemical workstation or other power supplys, with the positive and negative electrode of graphite rod as working electrode, take the dimethyl carbonate solution of lithiumbromide and lithium perchlorate as ionogen, the concentration of lithium ion is 1.6mol/L, and the mol ratio of lithiumbromide and lithium perchlorate is 9: 1, discharge and recharge operation, applying voltage is-the 3-3 volt, discharges and recharges operation, carries out ultrasonic to electrolytic solution in the electrolyzer simultaneously.In the process that discharges and recharges, make the insertion and the release that circulate in the carbon-coating of lithium ion in electrode, so that carbon-coating becomes is more and more loose, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution.The graphite layers peeled off is apart from becoming large in the process that discharges and recharges, then these graphite flakes of peeling off are carried out ultrasonicly, can obtain the good Graphene of dispersity.To solution or the Graphene solid that the Graphene that strips down filters, washing can obtain Graphene.
Embodiment 11
In the work system of a typical electrochemical workstation, provide energy derive by electrochemical workstation or other power supplys, with the positive and negative electrode of graphite rod as working electrode, take the DMF solution of chlorination lithium and lithium perchlorate as ionogen, the concentration of lithium ion is 1mol/L, the mol ratio of lithium chloride and lithium perchlorate is 1: 9, discharges and recharges operation, applies voltage to be-the 9-9 volt, discharge and recharge operation, carry out ultrasonic to electrolytic solution in the electrolyzer simultaneously.In the process that discharges and recharges, make the insertion and the release that circulate in the carbon-coating of lithium ion in electrode, so that carbon-coating becomes is more and more loose, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution.The graphite layers peeled off is apart from becoming large in the process that discharges and recharges, then these graphite flakes of peeling off are carried out ultrasonicly, can obtain the good Graphene of dispersity.To solution or the Graphene solid that the Graphene that strips down filters, washing can obtain Graphene.
Embodiment 12
In the work system of a typical electrochemical workstation, provide energy derive by electrochemical workstation or other power supplys, with the positive and negative electrode of graphite rod as working electrode, N with lithiumbromide and lithium perchlorate, the mixing solutions of N-N,N-DIMETHYLACETAMIDE and water is ionogen, the concentration of lithium ion is 0.8mol/L, the mol ratio of lithiumbromide and lithium perchlorate is 4: 6, N, N-N,N-DIMETHYLACETAMIDE and water weight ratio 1: 9 discharge and recharge operation, apply voltage to be-the 7-7 volt, discharge and recharge operation, carry out ultrasonic to electrolytic solution in the electrolyzer simultaneously.In the process that discharges and recharges, make the insertion and the release that circulate in the carbon-coating of lithium ion in electrode, so that carbon-coating becomes is more and more loose, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution.The graphite layers peeled off is apart from becoming large in the process that discharges and recharges, then these graphite flakes of peeling off are carried out ultrasonicly, can obtain the good Graphene of dispersity.To solution or the Graphene solid that the Graphene that strips down filters, washing can obtain Graphene.
Embodiment 13
In the work system of a typical electrochemical workstation, provide energy derive by electrochemical workstation or other power supplys, with the positive and negative electrode of graphite rod as working electrode, take the mixing solutions of the butyleneglycol of lithium perchlorate and water as ionogen, the concentration of lithium ion is 2mol/L, the mol ratio of lithiumbromide and lithium perchlorate is 4: 6, butyleneglycol and water weight ratio 9: 1 discharge and recharge operation, apply voltage to be-the 7-7 volt, discharge and recharge operation, carry out ultrasonic to electrolytic solution in the electrolyzer simultaneously.In the process that discharges and recharges, make the insertion and the release that circulate in the carbon-coating of lithium ion in electrode, so that carbon-coating becomes is more and more loose, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution.The graphite layers peeled off is apart from becoming large in the process that discharges and recharges, then these graphite flakes of peeling off are carried out ultrasonicly, can obtain the good Graphene of dispersity.To solution or the Graphene solid that the Graphene that strips down filters, washing can obtain Graphene.
Claims (18)
1. the preparation method of a Graphene, it is characterized in that the positive and negative electrode of graphite rod as working electrode, with the electrolyte solution of lithium ion as electrolytic solution, applying under the voltage effect, discharge and recharge operation, Graphite Electrodes is peeled off become the thin graphite flake that is rich in lithium ion and be dispersed in the electrolytic solution, the electrolytic solution of graphitiferous thin slice is carried out supersound process, through the solution or the Graphene solid that filter, washing can obtain Graphene.
2. according to claim 1 preparation method, wherein said electrolytic solution to the graphitiferous thin slice carries out supersound process and carries out synchronously in electrolyzer with electrolytic reaction.
3. according to claim 1 preparation method, wherein said electrolytic solution to the graphitiferous thin slice carries out supersound process and carries out after electrolytic reaction is finished.
4. according to claim 1 preparation method, the electrolyte solution of wherein said lithium ion is the solution of lithium halide or lithium perchlorate, or the mixing solutions of lithium halide and lithium perchlorate.
5. according to claim 3 preparation method, wherein said lithium halide refers to lithium chloride, lithiumbromide and lithium iodide.
6. according to claim 3 preparation method, described lithium halide is any mixture of one-component or lithium chloride, lithiumbromide and lithium iodide.
7. according to claim 3 preparation method, wherein said lithium halide refers to lithium chloride.
8. according to claim 3 preparation method, the mol ratio of lithium halide and lithium perchlorate is 1: 9～9: 1 in the mixing solutions of wherein said lithium halide and lithium perchlorate.
9. according to claim 3 preparation method, the mol ratio of lithium halide and lithium perchlorate is 4: 6～6: 4 in the mixing solutions of wherein said lithium halide and lithium perchlorate.
10. according to claim 3 preparation method, electrolyte solution is the aqueous solution of lithium ion.
11. preparation method according to claim 3, electrolyte solution is the organic solvent solution of lithium ion.
12. preparation method according to claim 3, electrolyte solution is the water of lithium ion and the mixing solutions of organic solvent.
13. according to claim 12 or 13 preparation method, described organic solvent refers to methylcarbonate, DMF, ethanol, ethylene glycol, propylene glycol, butyleneglycol, trichloromethane, methylene dichloride, acetonitrile.
14. preparation method according to claim 14, described organic solvent refers to methylcarbonate.
15. preparation method according to claim 14, described organic solvent refers to ethanol.
16. preparation method according to claim 1, wherein said working electrode positive and negative electrode is Graphite Electrodes.
17. preparation method according to claim 1, wherein said to apply voltage be-10～10 volts.
18. preparation method according to claim 1, wherein said to apply voltage be-8～8 volts.
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