CN101559941B - Method for preparing graphite alkenyl nanometer materials by electron beam irradiation method - Google Patents
Method for preparing graphite alkenyl nanometer materials by electron beam irradiation method Download PDFInfo
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- CN101559941B CN101559941B CN2009100520429A CN200910052042A CN101559941B CN 101559941 B CN101559941 B CN 101559941B CN 2009100520429 A CN2009100520429 A CN 2009100520429A CN 200910052042 A CN200910052042 A CN 200910052042A CN 101559941 B CN101559941 B CN 101559941B
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Abstract
The invention relates to a method for preparing graphite alkenyl nanometer materials by an electron beam irradiation method. The method comprises the following steps: firstly, oxidizing natural graphite to obtain oxidized graphite; secondly, realizing the stripping between layers of the oxidized graphite by ultrasonic sound at the state of solution; and finally reducing the oxidized graphite through certain dosage of electron beam irradiation, and obtaining the graphite alkenyl nanometer materials. The method has simple preparation process, short preparation period and high yield, can be operated at normal temperature, does not add any catalyst and chemical initiator, and can be applied on a large scale.
Description
Technical field
The present invention relates to a kind of preparation method of graphite alkenyl nanometer materials.Particularly a kind of electron beam irradiation legal system is equipped with the method for the graphite alkenyl nanometer materials of accurate two-dirnentional structure, belongs to electrochemistry and field of material synthesis technology.
Background technology
Lithium-ion secondary cell has advantages such as high-energy-density, high working voltage and long lifetime, has been widely used in portable electronics such as mobile telephone, notebook computer.Along with the continuous development of electromobile, advanced electronics, require to be equipped with power supply and have higher storage volume and cycle life.Commercial high-graphitized carbon negative pole material shows lower lithium storage content (＜372mAh/g, LiC owing to limited lithium stored position in the carbon hexahedron lattice of sp2 hydridization
6), more and more can not satisfy the requirement of technical development, seeking the excellent novel carbon negative pole material of height ratio capacity and cycle performance becomes one of the central task in current electrochemical energy investigation of materials field.
Graphene is a kind of accurate two-dimensional nanostructure of monatomic thickness of carbon; It is the mono-layer graphite sheet of the bi-dimensional cellular shape grid that closely is arranged in by the sp2 carbon atom, and the grapheme material that people prepare in the laboratory much is to pile up the accurate two-dimensional nano sheet (being no more than 10 layers usually) that forms by several layers of single-layer graphene.With its good electrical conductivity, chemicalstability and wide electrochemical window can well be used it in heavy body lithium storage materials field.
Preparation method of graphene mainly contains three kinds: the one, and the method for heating silit SiC; The 2nd, the mechanically peel method, nearly all perfect graphene film all utilizes above-mentioned two kinds of methods preparation; The 3rd, chemical synthesis, it is a kind of comparatively gentle synthetic route, by a lot of chemical and Condensed Matter Physics fields of being applied to.Chemical synthesis generally is to utilize strong oxidizer with graphite oxidation in solution; Utilize ultransonic method that graphite linings is peeled off then; Form graphene oxide, and then graphene oxide is reduced, re-assemblies and obtain various graphene-based materials with some means.Much human is utilized hydrazine hydrate aqueous solution reduction, and perhaps pyrolysis reductive method prepares the graphene nano material, and still, Hydrazine Hydrate 80 has severe toxicity, and the recovery time long (24 hours), process efficiency is low and the problem of environmental protection aspect arranged.The pyrolysis reduction also needs the long time usually, and efficient is low.
Summary of the invention
The objective of the invention is to overcome the problem that exists in the prior art, provide a kind of electron beam irradiation reduction method to prepare the method for graphite alkenyl nanometer materials.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of method of preparing graphite alkenyl nanometer materials by electron beam irradiation method is characterized in that the concrete steps of this method are:
A. at first, with Potassium Persulphate (K
2S
2O
8) 2.5g, Vanadium Pentoxide in FLAKES (P
2O
5) 2.5g, be dissolved in the 12ml vitriol oil, be heated to 80 ℃; Then the 3g natural graphite is added above-mentioned solution, be incubated 80 ℃ 4.5 hours; Be cooled to room temperature, after the dilution of 500ml deionized water, hold over night; Filter, with 0.2mm strainer elimination residual acid; Dry in 60 ℃ of vacuum drying ovens;
B. step a products therefrom is dissolved in the 120ml vitriol oil, under condition of ice bath, slowly adds 15g potassium permanganate in the solution; 35 ℃ of constant temperature stirred 2 hours, slowly diluted with 250ml water again, left standstill 2 hours; Add the dilution of 700ml water, 20mlH
2O
2(30%) adds above-mentioned solution; Use 1: 10 HCl solution 1L washing after the filtration again; Be dissolved in less water or the ethanol, after ultrasonic 20-30 minute, washing is filtered, and separates, and must precipitate for use;
C. get step b gained deposition 1.0g, drip the 1-2ml absolute ethyl alcohol, ultra-sonic dispersion 5 minutes adds the 50ml deionized water, 5ml Virahol, ultrasonic 15 minutes; Above-mentioned solution is poured in the vita envelope, and through electron beam irradiation, irradiation dose is 140kGy with above-mentioned solution; Then with the product behind the centrifugation method separation irradiation; With washed with de-ionized water 2 times, clean 2 times in 60 ℃ of vacuum dry 8 hours again with absolute ethyl alcohol; With the product grind into powder of oven dry, obtain graphene nanometer sheet at last.
Above-mentioned free-radical scavengers be Virahol, acetone or superoxide-dismutase (Superoxide Dismutase, SOD).
Above-mentioned steps c is with carrying out radiation treatment after the sealing of step b gained solution.
The preparation of graphene oxide sees also Yuxi Xu etc. at J.AM.CHEM.SOC., preparing described in 130 (18), 5856 (2008).In brief, utilize the vitriol oil, Potassium Persulphate, Vanadium Pentoxide in FLAKES and potassium permanganate, form graphite oxide, utilize ultransonic method to peel off then, through washing, filter, separate between aluminum oxide/graphite layer and the layer with the natural graphite oxidation, take out precipitate for use;
Compare with prior art, the inventive method has following conspicuous outstanding substantive distinguishing features and remarkable advantage is: the inventive method preparation technology is simple, can operate at normal temperatures, does not add any catalyzer and chemical initiator, and preparation cycle is short; Output is big, and productive rate is high, but sizable application.This method not only can prepare pure graphene nanometer sheet, also can be through in solution, adding other oxide precursors, and one-time reaction prepares various oxide nano particles compound graphite alkenyl nanometer materials.The graphene nanometer sheet that this method prepares, superior performance has high reversible lithium storage capacity, especially does the negative electrode active material in the electric energy storage device, has heavy body and stable cycle performance, is fit to do large value capacitor and serondary lithium battery.Thereby the preparation that the electron beam irradiation method applies to graphene nanometer sheet there are extremely wide research and application prospect.
The rumbatron that the inventive method adopts, the energy of its accelerated electron are 0.1 to 5MeV, and electronic beam current intensity is 0.1 to 100mA adjustable.
Description of drawings
The XRD figure spectrum of Fig. 1 electron beam irradiation reductive graphene nanometer sheet.
The TEM picture of Fig. 2 electron beam irradiation reductive graphene nanometer sheet.
The HRTEM picture of Fig. 3 electron beam irradiation reductive graphene nanometer sheet.
The charge and discharge cycles curve of Fig. 4 electron beam irradiation reductive graphene nanometer sheet.
Embodiment
Be discussed further in afterwards of the present invention in conjunction with embodiment now:
Embodiment one: at first, and with Potassium Persulphate (K
2S
2O
8) 2.5g, Vanadium Pentoxide in FLAKES (P
2O
5) 2.5g, be dissolved in the 12ml vitriol oil, be heated to 80 ℃; Then the 3g natural graphite is added above-mentioned solution, be incubated 80 ℃ 4.5 hours; Be cooled to room temperature, after the dilution of 500ml deionized water, hold over night; Filter, with 0.2mm strainer elimination residual acid; Dry in 60 ℃ of vacuum drying ovens; Above-mentioned product is dissolved in the 120ml vitriol oil, under condition of ice bath, slowly adds 15g potassium permanganate in the solution; 35 ℃ of constant temperature stirred 2 hours, slowly diluted with 250ml water again, left standstill 2 hours; Add the dilution of 700ml water, 20mlH
2O
2(30%) adds above-mentioned solution; Use 1: 10 HCl solution 1L washing after the filtration again; Be dissolved in less water or the ethanol, after ultrasonic 20-30 minute, washing is filtered, and separates, and must precipitate for use; Then get deposition 1.0g, drip the 1-2ml absolute ethyl alcohol, ultra-sonic dispersion 5 minutes adds the 50ml deionized water, 5ml Virahol, ultrasonic 15 minutes; Above-mentioned solution is poured in the vita envelope, and through electron beam irradiation, irradiation dose is 140kGy with above-mentioned solution; Then with the product behind the centrifugation method separation irradiation; With washed with de-ionized water 2 times, clean 2 times in 60 ℃ of vacuum dry 8 hours again with absolute ethyl alcohol; With the product grind into powder of oven dry, obtain graphene nanometer sheet at last.
Fig. 1, Fig. 2, Fig. 3 are respectively the XRD figure spectrums of graphene nanometer sheet of the accurate two-dirnentional structure of electron beam irradiation method preparation, and TEM picture and HRTEM picture can prove therefrom that what prepare is graphene nanometer sheet.
The chemical property of material is tested by following method: with the graphene nanometer sheet that makes and PTFE (tetrafluoroethylene, 20wt%), uniform mixing is processed film on to roller, is forcing together with copper mesh, as the positive pole of battery; As negative pole, barrier film is the capillary polypropylene material with metallic lithium; Electrolytic solution is to be dissolved in ethene carbonic ether (EC), propylene carbonate (DMC) and the ethyl-carbonate (DEC) formulatedly by LiPF6, and the concentration of LiPF6 is 1.0mol/L, and the mass ratio of EC, DMC and DEC is 1: 1: 1.In being full of the glove box of argon gas, assemble simulated battery.Voltage range during the battery charging and discharging test is 0.005～3V, and current density is 50mA/g.Fig. 4 is the charging and discharging curve of graphene nanometer sheet, and test result shows: the initial charge capacity of material is 1051mAh/g, and the charging capacity after 15 circulations is 783mAh/g, and its capability retention is 75%.
Claims (1)
1. the method for a preparing graphite alkenyl nanometer materials by electron beam irradiation method is characterized in that the concrete steps of this method are:
A. at first, with Potassium Persulphate (K
2S
2O
8) 2.5g, Vanadium Pentoxide in FLAKES (P
2O
5) 2.5g, be dissolved in the 12ml vitriol oil and be mixed with solution A, be heated to 80 ℃; Then the 3g natural graphite is added in the above-mentioned solution A, be incubated 80 ℃ 4.5 hours; Be cooled to room temperature, after the dilution of 500ml deionized water, hold over night; Filter, with 0.2mm strainer elimination residual acid; Dry in 60 ℃ of vacuum drying ovens;
B. step a products therefrom is dissolved in the 120ml vitriol oil, under condition of ice bath, slowly adds 15g potassium permanganate in the solution; 35 ℃ of constant temperature stirred 2 hours, slowly diluted with 250ml water again, left standstill 2 hours; Add the dilution of 700ml water, 20ml30%H
2O
2Add above-mentioned solution; Use 1: 10 HCl solution 1L washing after the filtration again; Be dissolved in less water or the ethanol, after ultrasonic 20-30 minute, washing is filtered, and separates, and must precipitate for use;
C. get step b gained deposition 1.0g, drip the 1-2ml absolute ethyl alcohol, ultra-sonic dispersion 5 minutes adds the 50ml deionized water, and the 5ml Virahol ultrasonic 15 minutes, is mixed with solution B; Above-mentioned solution B is poured in the vita envelope, and through electron beam irradiation, irradiation dose is 140kGy with above-mentioned solution B; Then with the product behind the centrifugation method separation irradiation; With washed with de-ionized water 2 times, clean 2 times in 60 ℃ of vacuum dry 8 hours again with absolute ethyl alcohol; With the product grind into powder of oven dry, obtain graphene nanometer sheet at last.
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| CN108047535A (en) * | 2017-12-19 | 2018-05-18 | 湖北洋田塑料制品有限公司 | A kind of high-tension cable conductive shield material and preparation method thereof |
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