CN106853965A - A kind of preparation method of negative material Graphene and electrochemical property test method - Google Patents

A kind of preparation method of negative material Graphene and electrochemical property test method Download PDF

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CN106853965A
CN106853965A CN201611270089.9A CN201611270089A CN106853965A CN 106853965 A CN106853965 A CN 106853965A CN 201611270089 A CN201611270089 A CN 201611270089A CN 106853965 A CN106853965 A CN 106853965A
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graphene
negative
graphene oxide
necked flask
potassium permanganate
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王高军
王象
丁伟
钟琴
姜莉莉
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University of Shaoxing
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416Systems
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/40Electric properties
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses the preparation method and its electrochemical property test method of a kind of negative material Graphene, including:Graphite powder and sodium nitrate are weighed, and measures the concentrated sulfuric acid and be mixed in there-necked flask, reacted under the conditions of ice-water bath;Weigh again in potassium permanganate addition there-necked flask, start to adjust temperature;Potassium permanganate is added at twice in there-necked flask, control temperature;Frozen water is added to allow to cool to room temperature;Then 30% hydrogenperoxide steam generator is added dropwise to be washed;Centrifugation is carried out, lower floor's solids of sedimentation is taken out, cyclic washing is carried out, the solid product for obtaining is vacuum dried, and is ground standby after taking-up.Specific discharge capacity of the graphene oxide of the invention as the negative material of lithium battery under 0.1C has 403.4mAh/g.The Graphene performance prepared further with hydro-thermal solvothermal method is more stable, and the specific discharge capacity under 0.1C has 782.8mAh/g, and capability retention is higher.

Description

A kind of preparation method of negative material Graphene and electrochemical property test method
Technical field
The invention belongs to negative material preparing technical field, more particularly to a kind of negative material Graphene preparation method and Its electrochemical property test method.
Background technology
With the development of science and technology, 21 century enter the epoch of informationization already, intelligent equipment just gradually moves towards Huge numbers of families.Such as present smart mobile phone, updating to be even more becomes accustomed to, because its function is more powerful, therewith Its energy consumption is also mutually strained greatly, and the problem of mobile phone continuation of the journey annoyings users always.So the volumetric properties of battery become intelligence The difficulty that must be captured in energy mobile phone development.Additionally, now in human society using fossil fuel as main in energy system Part, and this fossil fuel is the drawbacks of to human lives also band, some are very important.Firstly, since combustion of fossil fuel meeting Substantial amounts of toxic gas and greenhouse gases are produced, these gases cause global warming in being largely discharged into air, so as to threaten The survival and development of the mankind are arrived;Secondly, this non-renewable energy can trigger energy crisis sooner or later, so constantly to enter Suitable energy substitution product is found in row research.For populous nation, energy problem is even more the task of top priority, and environmental protection It is extremely urgent.The one of the main reasons of haze problem aggravation in recent years is exactly that the excessive emissions of vehicle exhaust cause, if Ev industry can be greatly developed will to be very beneficial for solving the problems, such as the haze that the country is faced at present.But, as main Because of its high cost, the reason such as specific energy is small governs the development of the ev industry of China to the lithium ion battery of electrokinetic cell. Used as a kind of Novel Carbon Nanomaterials, Graphene has the advantages that big specific surface area, electric conductivity and good heat conductivity, in battery storage Energy aspect has very big potentiality.Graphene can as the negative material of lithium ion battery, with capacity very high, and Its electron mobility and thermal conductivity for just possessing superelevation at room temperature.But, high-quality Graphene is but to be difficult to be obtained, and It is difficult to a large amount of productions.There are many methods for preparing Graphene at present, but it is high-purity so as to prepare how to improve experimental technique The Graphene of degree is all the time the target of numerous scientist struggles.Preparing the conventional method of Graphene has:(1) mechanical stripping Method, it is exactly that graphene sheet layer is peeled off from the surface of native graphite using mechanical force that this kind of method prepares Graphene.Graphite It is to be combined with Van der Waals force between lamella, and Van der Waals force is relatively weak, interaction force also very little, therefore be easy to relative Slide and depart from, this exactly provides theoretical foundation for mechanical stripping method prepares Graphene.Geim et al. used glue in 2004 Repeatedly tear-off graphite is brought, and the Graphene of individual layer has successfully been obtained by this simple method.The initial quilt of Graphene When being made of mechanical stripping method, its thickness probably has tens nanometers, but with the constantly improve of preparation technology, graphene film The thickness of layer is gradually reduced and specific surface area gradually increases.The preparation technology of mechanical stripping method is most simple, and product graphite The structural behaviour of alkene is closest to preferable graphene sheet layer.But it is low that Graphene efficiency is prepared with the method, and it compares table Area very little, may be only available for laboratory research and cannot put into industrialized production.(2) chemical vapour deposition technique (CVD) the graphene sheet layer product purity that, the method is prepared is big compared with high, specific surface area, has become high-quality graphene The main method of preparation.Graphene growth is extremely complex heterogeneous catalytic reaction body on the surface of metallic catalyst (CVD) System.(3) oxidation-reduction method, natural crystalline flake graphite is normal by carry out reduction after the oxidation intercalation of strong acid again to be prepared into Graphene The method for preparing Graphene.Brodie in 1860 etc. is using the strong oxidation of concentrated nitric acid and potassium chlorate to natural scale stone Ink carries out intercalation processing, and graphene oxide has been obtained.Afterwards, Staudenmaier and Aksay etc. adds again in system before Enter other strong acid and form mixing acid system, native graphite is processed using similar method, be similarly obtained graphite oxide Alkene.It is exactly Hummers methods to prepare graphene oxide most common method, the method be first by the native graphite of material powder shape, It is placed in there-necked flask together with three kinds of material mixings of sodium nitrate solid and the concentrated sulfuric acid, and it is carefully positioned in cooling water, And then take out a small amount of oxidant potassium permanganate solid to pour into slowly in above-mentioned flask, afterwards by flask in appropriate temperature Lower continuous heating, allows it fully to react, and a small amount of hydrogenperoxide steam generator is added dropwise again after oxidation reaction terminates and goes to rinse flask The complete oxidant of unreacted is inside gone back, suction filtration operation is carried out finally by filter flask, then washed with water, centrifuge tube is placed on afterwards Inside carry out centrifugally operated, you can obtain graphene oxide.Depth intercalation is carried out to graphite by chemical oxidization method, is prepared Graphene sheet layer is few, specific surface area is big.But substantial amounts of oxy radical is but introduced into, the inside of their meeting heavy damage Graphenes Structure, causes a large amount of defects, so as to have influence on its some performances, therefore also needs to repair graphene oxide internal structure It is multiple, its oxy radical is removed, reduce its surface defect.(4) epitaxial growth method, SiC epitaxial growth methods prepare Graphene and are exactly Corresponding Graphene crystal is allowed to grow on top on its crystal structure.Its principle is in certain high temperature or true Si atoms are removed under conditions of sky, then carbon atom carries out being self-assembly of the graphite of a fixed structure on crystal structure Alkene.Berger etc. using above-mentioned preparation condition by 6H-SiC silicon atom remove, relief graphite on top voluntarily assemble after Form Graphene.Subsequent Emtsev etc. reports surface of SiC epitaxial growth in atmospheric conditions and goes out Graphene, this Graphene Carrier mobility be 2 × 105cm2V-1S-1.Juang etc. declines for the reaction temperature for causing epitaxial growth, in advance in SiC bases Layer of Ni film is plated on bottom, Graphene can be thus prepared in the environment of low temperature.Graphene prepared by SiC epitaxial growth methods has Area is big, the characteristics of quality is high, such that it is able to be widely used in fields such as integrated circuits.
Graphene storage lithium has height ratio capacity and powerful advantage, but also has the disadvantage that:(1) low coulombic efficiency: Electrolyte can decompose during circulation, can form electrochemical interface film, so as to cause portion capacity to lose;(2) initial capacity Decay is fast, and typically after ten circulate several times, capacity is just gradually stablized.Graphene is since being found just to be closed by people extensively always Note, on prepare its method also constantly improve in, exploration developing stage of the domestic Graphene industry also in volume production.Mesh Come to see, it is feasible to produce Graphene in batches by carrying out redox method to graphite.But prepared by the technique Graphene, its internal unstable hydraulic performance decline for easily being destroyed, causing Graphene of molecular structure;Additionally, Graphene is also Agglomeration can occur in graphene dispersing solution prepared by the method, it is inclined that it there are many performances all to occur with theoretical value Move.
In sum, there is structure and lack in the graphene oxide and Graphene that prepared by the preparation method of existing graphene oxide Fall into, efficiency for charge-discharge is poor, and molecular structure is unstable, the problems such as dispersion effect is poor.
The content of the invention
Preparation method and its electrochemical property test side it is an object of the invention to provide a kind of negative material Graphene Method, it is intended to which the graphene oxide and Graphene for solving the preparation method preparation of existing graphene oxide have fault of construction, fill Discharging efficiency is poor, and molecular structure is unstable, dispersion effect difference the problems such as.
The present invention is achieved in that a kind of preparation method of negative material Graphene, the negative material Graphene Preparation method is comprised the following steps:
Step one, weighs 3g graphite powders and 1.5g sodium nitrate, and measures the concentrated sulfuric acid and be mixed in there-necked flask, Reacted under the conditions of ice-water bath, and be stirred continuously;Again with electronic balance weigh 9g potassium permanganate be divided into several aliquots it is careful plus Enter in there-necked flask, control Wen Du≤20 DEG C of ice-water bath, be stirred continuously with magneton with this understanding, when oxidant permanganic acid After potassium addition is finished, start to adjust temperature;
Step 2, then potassium permanganate is weighed with electronic balance, potassium permanganate disposably being added in there-necked flask, control is warm Degree;After after its reaction completely, frozen water is added to allow to cool to room temperature toward the reaction solution in above-mentioned there-necked flask;
Step 3, is then added dropwise 30% hydrogenperoxide steam generator and is washed;Placing reaction liquid into afterwards in centrifuge tube is carried out Centrifugation, takes out lower floor's solids of sedimentation after filtering, respectively with deionized water, hydrochloric acid, absolute ethyl alcohol carries out cyclic washing, obtains Solid product be vacuum dried, ground standby after taking-up.
Further, in the step one, 3g graphite powders and 1.5g sodium nitrate are weighed, and measures the 69mL concentrated sulfuric acids and mixed Close in there-necked flask;
When oxidant potassium permanganate addition finish after, start to adjust the temperature to 35 DEG C, relief its reaction 7h.
Further, in the step 2, its temperature is controlled for 35 DEG C, allow it to react 12h with this understanding;Treat that it has reacted Quan Hou, adds 400mL frozen water to allow to cool to room temperature toward the reaction solution in above-mentioned there-necked flask.
Further, in the step 3, the hydrogenperoxide steam generators of 3mL 30% are added dropwise and are washed;Place reaction liquid into afterwards Centrifugation is carried out in centrifuge tube, lower floor's solids of sedimentation is taken out after filtering, 200ml deionized waters, the salt of 30% concentration are used respectively Acid, absolute ethyl alcohol carries out cyclic washing, and the solid product for obtaining is vacuum dried at 60 DEG C, is ground standby after taking-up With.
Another object of the present invention is to provide oxygen prepared by a kind of preparation method using the negative material Graphene Graphite alkene.
Another object of the present invention is to provide a kind of Graphene prepared using the graphene oxide.
Another object of the present invention is to provide a kind of battery prepared using the graphene oxide.
Another object of the present invention is to provide a kind of electrochemical property test method of the graphene oxide, the electricity Chemical property method of testing includes:
(1) it is 9 according to mass ratio by graphene oxide and PTFE:1 is well mixed, and adds ultrasonic disperse after 10ml ethanol 10min, is transferred in baking oven in 30min is kept at 70 DEG C, then takes out and is rolled into electrode slice, is covered in nickel foam, in hand Button cell is assembled into by negative pole of metal lithium sheet in casing, after taking-up, using Chi760E electrochemical workstations, using circulation Volt-ampere method of testing, scanned at different rates in current potential 0-3V scopes, from 2mV/s to 10mV/s during figure present Similitude, the part oxy radical on graphene oxide can occur redox reaction with lithium ion;
(2) redox reaction of graphene oxide, the specific capacity of charging is 390mAh/g, and the specific capacity of electric discharge is 403.4mAh/g, efficiency for charge-discharge is 103.4%;103.4% efficiency when graphene oxide is by 0.1C discharge and recharges is to 1C charge and discharges 96.6% efficiency when electric.
The preparation method and its electrochemical property test method of the negative material Graphene that the present invention is provided, prepare Graphene Method be chemistry redox method, be dispersed in being prepared into water and organic solvent 1-METHYLPYRROLIDONE (NMP) afterwards Slurry, then carries out ultrasonic stripping, and the Graphene slurry after most being concentrated through distillation treatment afterwards, dispersion effect is preferable.This hair It is bright that Graphene is prepared by redox method, it is characterized with XRD and SEM then, based on above-mentioned experimental result, can To judge that graphene oxide possesses certain capacity as the negative material of lithium battery, part oxy radical can occur oxidation also Original reaction, its specific discharge capacity under 0.1C has 403.4mAh/g, further with stone prepared by hydro-thermal-solvothermal method Black alkene is more stable, and its specific discharge capacity under 0.1C has 782.8mAh/g, and its capability retention is higher.It is improved Hummers prepares the amount that graphene oxide increased sodium nitrate and potassium permanganate than traditional Hummers methods, makes the oxygen of graphite Change more completely, while using the method for oxidation of secondary addition potassium permanganate, can become much larger the interlamellar spacing of graphite, follow-up stone The stripping of layer of ink is more thorough, obtains the few Graphene of lamella.
Brief description of the drawings
Fig. 1 is the preparation method flow chart of negative material Graphene provided in an embodiment of the present invention.
Fig. 2 is the XRD spectrum schematic diagram of graphene oxide provided in an embodiment of the present invention.
Fig. 3 is the XRD spectrum schematic diagram of raw graphite provided in an embodiment of the present invention.
Fig. 4 is the SEM spectrum schematic diagram of graphene oxide provided in an embodiment of the present invention.
Fig. 5 is the cyclic voltammetric collection of illustrative plates schematic diagram of graphene oxide provided in an embodiment of the present invention.
Fig. 6 is the 0.1C charging and discharging curve schematic diagrames of graphene oxide provided in an embodiment of the present invention.
Fig. 7 is the charging and discharging curve figure schematic diagram of graphene oxide 1C provided in an embodiment of the present invention.
Fig. 8 is the XRD spectrum schematic diagram of Graphene provided in an embodiment of the present invention.
Fig. 9 is the SEM spectrum schematic diagram of Graphene provided in an embodiment of the present invention.
Figure 10 is the cyclic voltammetric collection of illustrative plates schematic diagram of Graphene provided in an embodiment of the present invention.
Figure 11 is the charging and discharging curve schematic diagram of Graphene 0.1C provided in an embodiment of the present invention.
Figure 12 is the charging and discharging curve schematic diagram of Graphene 0.1C to 0.4C provided in an embodiment of the present invention.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.
Application principle of the invention is explained in detail below in conjunction with the accompanying drawings.
As shown in figure 1, the preparation method of negative material Graphene provided in an embodiment of the present invention is comprised the following steps:
S101:3g graphite powders and 1.5g sodium nitrate are weighed, and measure the 69mL concentrated sulfuric acids and be mixed in there-necked flask, Reacted under the conditions of ice-water bath, and be stirred continuously;Accurately weighing 9g potassium permanganate with electronic balance again, to be divided into several aliquots small In the above-mentioned there-necked flask of addition of the heart, Wen Du≤20 DEG C of ice-water bath are controlled, be stirred continuously with magneton with this understanding, when oxygen Agent potassium permanganate addition finish after, beginning slowly adjust the temperature to 35 DEG C, relief its react about 7h;
S102:9g potassium permanganate is accurately weighed with electronic balance again, next by load weighted potassium permanganate quick one Secondary property is added in above-mentioned there-necked flask, controls its temperature for 35 DEG C, allows it to react 12h with this understanding;After its reaction is complete, About 400mL frozen water is added to allow to cool to room temperature toward the reaction solution in above-mentioned there-necked flask;
S103:Then the hydrogenperoxide steam generators of 3mL 30% are slowly added dropwise to be washed;Centrifuge tube is placed reaction liquid into afterwards Centrifugation is inside carried out, lower floor solids of sedimentation is taken out after filtering, use 200ml deionized waters respectively, the hydrochloric acid of appropriate 30% concentration, Appropriate absolute ethyl alcohol carries out cyclic washing, and the solid product for obtaining is vacuum dried at 60 DEG C, is ground standby after taking-up With.
Application principle of the invention is further described with reference to experiment.
1 experimental section
1.1 main chemical reagent and laboratory apparatus
The chemical raw material of table 1 (reagent)
The laboratory apparatus of table 2
1.2 improvement Hummers prepare graphene oxide
3g graphite powders and 1.5g sodium nitrate accurately are weighed, and measure the 69mL concentrated sulfuric acids and be mixed in there-necked flask, Reacted under the conditions of ice-water bath, and be stirred continuously.Accurately weighing 9g potassium permanganate with electronic balance again, to be divided into several aliquots small In the above-mentioned there-necked flask of addition of the heart, Wen Du≤20 DEG C of ice-water bath are controlled, be stirred continuously with magneton with this understanding, when oxygen Agent potassium permanganate addition finish after, beginning slowly adjust the temperature to 35 DEG C, relief its reaction about 7h, then with electronic balance standard 9g potassium permanganate really is weighed, is next quickly disposably added load weighted potassium permanganate in above-mentioned there-necked flask, controlled Its temperature is 35 DEG C, allows it to react 12h with this understanding.After after its reaction completely, toward the reaction solution in above-mentioned there-necked flask Add about 400mL frozen water to allow to cool to room temperature, be then slowly added dropwise the hydrogenperoxide steam generators of 3mL 30% and washed.Afterwards will Reaction solution is placed in carries out centrifugation in centrifuge tube, lower floor's solids of sedimentation is taken out after filtering, and 200ml deionized waters are used respectively, fits The hydrochloric acid of 30% concentration is measured, appropriate absolute ethyl alcohol carries out cyclic washing, and the solid product for obtaining is vacuum dried at 60 DEG C, Ground after taking-up standby.
The preparation of 1.3 Graphenes
Above-mentioned graphene oxide is carried out to reduce prepared Graphene using hydro-thermal-solvothermal method, specifically with water and Organic solvent (ethanol, n-butanol and ethylene glycol etc.) is configured to mixed solvent and stone will be aoxidized in reactor at 140 DEG C of temperature Black alkene carries out hydrothermal reduction, and wherein mixed solvent is according to volume ratio 5 by absolute ethyl alcohol and ethyl acetate:3 are prepared, and Graphene oxide is dispersed in absolute ethyl alcohol, is then mixed and is reacted 3h at 140 DEG C in a kettle., afterwards question response Kettle is filtered after being cooled to room temperature, and Graphene is obtained after being finally vacuum dried at 80 DEG C.
The preparation of 1.4 batteries
By negative material Graphene or Graphene, conductive agent carbon black and binding agent PTFE are according to mass ratio 8:1:1 is claimed , in beaker be uniformly mixed above-mentioned 3 kinds of materials afterwards by amount, surpasses it under Ultrasound Instrument after appropriate absolute ethyl alcohol is added dropwise Sound makes the more uniform of its mixing, and next drying makes it become pasty state at 80 DEG C, then is being put down it with hollow glass tube Compressing tablet is carried out on whole glass plate, it is rolled into the sheet of large area as far as possible, then intercept part piece with circular die Shape material is placed in button cell shell, and material is compacted in battery case at suitable pressures and then, by what is prepared Battery is placed in and 6h is dried in vacuum drying chamber, and the assembling of battery is finally carried out in glove box.
2. result and discussion
The sign of 2.1 graphene oxides
2.1.1 the structural characterization of graphene oxide --- XRD
Fig. 2 is the XRD of graphene oxide sample, is having diffraction maximum, the diffraction of graphene oxide positioned at 2 θ=24.85 ° Peak-to-peak shape is wider, and Fig. 3 is the XRD of graphite, and the characteristic diffraction peak of graphite is strong and sharp in figure, crystal formation is illustrated very well, with graphite Standard x RD figures it is not high compared to its diffracted intensity, illustrate that graphite is oxidized, its structure is caused by strong oxidizer destruction, and There is not (10 ° of diffraction maximum represents that graphene oxide is individual layer) in 10 ° or so of characteristic peaks, this explanation graphene oxide can It can be the structure of multilayer.
2.1.2 the morphology characterization of graphene oxide --- SEM
The graphene oxide sample of synthesis has been carried out sem test by this experiment.Fig. 4 is respectively to amplify 10000 times, SEM figures after 5000 times and 2000 times.It can be seen that prepared graphene oxide sample particle is larger from this three width figure, table Face is unsmooth, is covered with fold, there is many defects, groove, and the phenomenon of curling occurs in its edge, can be evident that it is multilayer Graphene oxide.
Chemical property of 2.2 graphene oxides in lithium battery
2.2.1 cyclic voltammetric research
Fig. 5 is the cyclic voltammetry curve of graphene oxide.Scanned at different rates in current potential 0-3V scopes, from figure As can be seen that figure presentation similitude during from 2mV/s to 10mV/s, only a pair more obvious redox peaks, Illustrate lithium ion insertion in the material and it is embedding go out process.There is a stronger reduction peak in 2.5V or so, this is first with battery It is corresponding that secondary charging and discharging curve has platform more long, and when electric potential scanning is carried out with 4mV/s, strong reduction peak fades away, and In 2.75V or so there is weaker reduction peak, and the small many of its area compared with reduction peak before.With reference to graphite oxide From the point of view of the charging and discharging curve of alkene, it can be deduced that conclusion, the part oxy radical on graphene oxide can occur oxygen with lithium ion Change reduction reaction, the redox peaks that such as 2.5V, 2.75V occur.
2.2.2 constant current charge-discharge performance study
Fig. 6 is first charge-discharge figure of the negative material Graphene under 0.1C.It can be seen that near 0.25V There is a charging platform, there is individual discharge platform near 1.5V, the redox reaction of graphene oxide is correspond to respectively.Charge Specific capacity be 390mAh/g, the specific capacity of electric discharge is 403.4mAh/g, and efficiency for charge-discharge is 103.4%.
Fig. 7 is first charge-discharge figure of the graphene oxide under 1C.It can be seen that having a charging in 1.25V Platform, there is individual discharge platform near 1.5V, and the redox reaction of graphene oxide is correspond to respectively.The specific capacity of charging is 44.58mAh/g, the specific capacity of electric discharge is 43.08mAh/g, and efficiency for charge-discharge is 96.6%.From above-mentioned two width charging and discharging curve figure In as can be seen that the efficiency of 103.4% efficiency when graphene oxide is by 0.1C discharge and recharges to during 1C discharge and recharges 96.6%, and Its specific discharge capacity drops to 43.08mAh/g by 403.4mAh/g, it may be possible to because the electrolyte in battery is decomposed, Form the decline that electrochemical interface film result in capacity.
The sign of 2.3 negative material Graphenes
2.3.1 the structural characterization of negative material Graphene --- XRD
Fig. 8 is the XRD of Graphene sample, is having diffraction maximum positioned at 2 θ=24.61 °, with graphene oxide XRD before Figure is compared, and diffraction maximum slightly strengthens, and illustrates that its part oxy radical is eliminated, and its diffracted intensity is compared with the XRD of graphite Seem weaker, it does not occur in 10 ° or so of characteristic peak, this explanation Graphene may be also the structure of multilayer.
2.3.2 the morphology characterization of negative material Graphene --- SEM
The graphene oxide sample of synthesis has been carried out sem test by this experiment.Fig. 9 is respectively to amplify 10000 times, SEM figures after 5000 times and 2000 times.It can be seen that prepared Graphene sample lamella is less from this three width figure, size compared with Greatly, surface is relatively smooth, and defect is less.
Chemical property of the 2.4 negative material Graphenes in lithium battery
2.4.1 cyclic voltammetric research
Figure 10 is the cyclic voltammetry curve of Graphene.Scanned at different rates in current potential 0-3V scopes, can from figure To find out, from 0.1mV/s to 1mV/s during figure there is similitude, respectively have a pair of redox peaks, if sweep speed Increasing its corresponding peak current also can be with increase.In the case where sweep speed is 0.1mV/s, the potential of oxidation peak is 1.69V, and its is right The potential of the reduction peak answered is 0.8V, and in the case where sweep speed is 1mV/s, the potential of oxidation peak is 1.85V, its corresponding reduction peak Potential be 0.64V.
2.4.2 constant current charge-discharge performance study
Figure 11 is Graphene first charge-discharge figure under 0.1C, as can be seen from the figure there is a chargin level near 1.0V Platform, there is individual discharge platform near 2V, and the redox reaction of Graphene is correspond to respectively.The specific capacity of charging is 746.2mAh/g, the specific capacity of electric discharge is 782.8mAh/g, and efficiency for charge-discharge is 95.3%.
Figure 12 is analyzed:Under 0.1C multiplying powers, discharge capacity is 782.8mAh/g;Under 0.2C multiplying powers, discharge capacity 583.9mAh/g;Under 0.4C multiplying powers, first time discharge capacity is 416.8mAh/g, and second discharge capacity is 258.4mAh/ g;When discharge current increases to 0.2C from 0.1C, capability retention is 74.5% during this;When discharge current from 0.1C When increasing to 0.4C, capability retention is 53.2% during this.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.

Claims (8)

1. a kind of preparation method of negative material Graphene, it is characterised in that the preparation method bag of the negative material Graphene Include following steps:
Step one, weighs 3g graphite powders and 1.5g sodium nitrate, and measures the concentrated sulfuric acid and be mixed in there-necked flask, in frozen water Reacted under the conditions of bath, and be stirred continuously;9g potassium permanganate is weighed with electronic balance be divided into several aliquots addition there-necked flasks again In, Wen Du≤20 DEG C of ice-water bath are controlled, it is stirred continuously with magneton with this understanding, when oxidant potassium permanganate addition is finished Afterwards, start to adjust temperature;
Step 2, then potassium permanganate is weighed with electronic balance, potassium permanganate is disposably added in there-necked flask, control temperature; After after its reaction completely, frozen water is added to allow to cool to room temperature toward the reaction solution in above-mentioned there-necked flask;
Step 3, is then added dropwise 30% hydrogenperoxide steam generator and is washed;Place reaction liquid into centrifuge tube afterwards and be centrifuged Precipitation, takes out lower floor's solids of sedimentation after filtering, respectively with deionized water, the hydrochloric acid of 30% concentration, absolute ethyl alcohol is washed repeatedly Wash, the solid product for obtaining is vacuum dried, ground standby after taking-up.
2. the preparation method of negative material Graphene as claimed in claim 1, it is characterised in that in the step one, weigh 3g graphite powders and 1.5g sodium nitrate, and measure the 69mL concentrated sulfuric acids and be mixed in there-necked flask;
When oxidant potassium permanganate addition finish after, start to adjust the temperature to 35 DEG C, relief its reaction 7h.
3. the preparation method of negative material Graphene as claimed in claim 1, it is characterised in that in the step 2, control Its temperature is 35 DEG C, allows it to react 12h with this understanding;After after its reaction completely, toward the reaction solution in above-mentioned there-necked flask 400mL frozen water is added to allow to cool to room temperature.
4. the preparation method of negative material Graphene as claimed in claim 1, it is characterised in that in the step 3, is added dropwise The hydrogenperoxide steam generators of 3mL 30% are washed;Placing reaction liquid into afterwards carries out centrifugation in centrifuge tube, taken out after filtering Lower floor's solids of sedimentation, uses 200ml deionized waters respectively, and the hydrochloric acid of 30% concentration, absolute ethyl alcohol carries out cyclic washing, and what is obtained consolidates Body product is vacuum dried at 60 DEG C, is ground standby after taking-up.
5. the graphite oxide that prepared by a kind of preparation method of negative material Graphene described in utilization claim 1~4 any one Alkene.
6. the Graphene that prepared by graphene oxide described in a kind of utilization claim 5.
7. the battery that prepared by graphene oxide described in a kind of utilization claim 5.
8. a kind of electrochemical property test method of graphene oxide as claimed in claim 5, it is characterised in that the electrochemistry Performance test methods include:
(1) it is 9 according to mass ratio by graphene oxide and PTFE:1 is well mixed, and adds ultrasonic disperse 10min after 10ml ethanol, It is transferred in baking oven in 30min is kept at 70 DEG C, then takes out and be rolled into electrode slice, is covered in nickel foam, in glove box Button cell is assembled into by negative pole of metal lithium sheet, after taking-up, using Chi760E electrochemical workstations, is surveyed using cyclic voltammetric Method for testing, scans at different rates in current potential 0-3V scopes;
(2) redox reaction of graphene oxide, the specific capacity of charging is 390mAh/g, and the specific capacity of electric discharge is 403.4mAh/g, efficiency for charge-discharge is 103.4%;103.4% efficiency when graphene oxide is by 0.1C discharge and recharges is to 1C charge and discharges 96.6% efficiency when electric;
(3) above-mentioned graphene oxide is carried out to reduce prepared Graphene using hydro-thermal-solvothermal method, specifically with water and having Machine solvent is configured to mixed solvent and graphene oxide is carried out into hydrothermal reduction in reactor at 140 DEG C of temperature, wherein mixing Solvent is according to volume ratio 5 by absolute ethyl alcohol and ethyl acetate:3 are prepared, and graphene oxide is dispersed in into anhydrous second In alcohol, then it is mixed and reacts 3h at 140 DEG C in a kettle., question response kettle is filtered after being cooled to room temperature afterwards, It is last that Graphene is obtained after vacuum drying at 80 DEG C.
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