CN102509643A - Graphene/carbon ball composite material, and preparation and application thereof - Google Patents
Graphene/carbon ball composite material, and preparation and application thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a graphene/carbon ball composite material, belonging to the technical field of composite materials. The method comprises the following steps of: obtaining a graphene oxide precursor solution in an ultrasonic stripping manner; carrying out hydro-thermal treatment of glucose under a certain temperature to obtain carbon balls; and then self-assembling and reducing graphene oxide and the carbon balls under a certain condition to obtain the graphene/carbon ball composite material. The composite material is used as an electrode material of a super-capacitor. Because graphene agglomeration can be effectively prevented through the carbon balls in the composite material, a graphene electric double layer capacitor can be well displayed, therefore, the composite material shows excellent electrochemical performance.
Description
Technical field
The invention belongs to field of compound material, relate to a kind of Graphene/carbon ball composite material; The present invention also relates to the preparation and the application in the preparation electrode of super capacitor thereof of this Graphene/carbon ball composite material simultaneously.
Background technology
Along with living standard improves day by day, environmental pollution and energy starved crisis have caused that people greatly pay close attention to.Ultracapacitor is claimed electrochemical capacitor again, is a kind of novel energy-storing device between traditional capacitor and battery.It has higher ratio electric capacity and energy density than traditional capacitor; Has higher power density than battery; But the especially big electric current of abrupt release; Have the charging interval short, charge efficiency is high, recycle characteristics such as long, memory-less effect of life-span and basic Maintenance free, its application prospect is boundless.As everyone knows; Electrode material is the core of ultracapacitor technical development; Should have suitable thermodynamic stability as the material of electrode material for super capacitor, and good electron, ionic conductivity, and in commercial application, require its cost low and in light weight.Material with carbon element is cheap and easy to get with it, the quality small specific surface is long-pending big, good conductivity, characteristics that kind is many, is the focus that people pay close attention in the application facet of electrode material always.
Graphene by one deck intensive be wrapped in the two dimensional crystal material with carbon element that the carbon atom on the honeycomb crystal lattice is formed; The fullerene that can warpage becomes zero dimension; Be rolled into the CNT of one dimension or be stacked to three-dimensional graphite, so Graphene is the elementary cell that constitutes other graphite materials.Compare with CNT, Graphene has more excellent character, for example, and good electrical conductivity (10
3– 10
4S/m), the specific area of super large (2630 m
2/ g), chemical property is stable and machinability etc., this makes it become than the better electrochemistry new forms of energy of CNT and transforms and the electrode material that stores.But in practical application, the effect of Van der Waals force is reunited easily or stacking and cause the not high result of actual specific electric capacity again it.Graphene-based composite material has then effectively overcome this difficult problem of Graphene; Because positive synergy makes other composition in the composite material effectively stop the reunion of Graphene; Thereby make the electric double layer capacitance of Graphene be able to good displaying, effectively raise the ratio electric capacity of whole material.
Summary of the invention
The object of the present invention is to provide a kind of Graphene/carbon ball composite material.
Another object of the present invention is to provide the preparation method of a kind of Graphene/carbon ball composite material.
A further object of the invention just provides the application of a kind of this Graphene/carbon ball composite material at the preparation electrode of super capacitor.
(1) preparation of Graphene/carbon ball composite material
The preparation method of Graphene of the present invention/carbon ball composite material comprises following processing step:
(1) preparation of graphene oxide presoma dispersion liquid: be scattered in the distilled water graphite oxide is ultrasonic, form the graphene oxide presoma dispersion liquid of concentration 0.2 ~ 0.4mg/ml;
(2) preparation of carbon ball: glucose is dissolved in the distilled water, and forming concentration is the glucose solution of 0.4 ~ 0.6mol/L, glucose solution is moved in the autoclave, in 160 ~ 180 ℃ of following hydrothermal treatment consists 4 ~ 7h again; Suction filtration, with ethanol, distilled water cyclic washing, drying obtains the carbon ball;
(3) preparation of carbon ball dispersion liquid: with above-mentioned carbon ball last ultrasonic being scattered in the distilled water of pulverizing, forming concentration is the carbon ball dispersion liquid of 0.1 ~ 0.2mg/ml;
(4) preparation of Graphene/carbon ball composite material: in above-mentioned graphene oxide presoma dispersion liquid, add hydrazine hydrate earlier, add carbon ball dispersion liquid under the strong agitation again, mix the back and transfer pH=9 ~ 10; The toluene that adds mixed system volume 7 ~ 10% is in 80 ~ 90 ℃ of 5 ~ 7h that reflux; After removing toluene products therefrom is filtered, with distilled water and ethanol cyclic washing, drying obtains Graphene/carbon ball composite material.
The addition of hydrazine hydrate is in the said graphene oxide presoma dispersion liquid: the volume ratio of graphite oxide quality and hydrazine hydrate is 100mg:1.5ml ~ 100mg:3ml, and the volume ratio of said graphene oxide presoma dispersion liquid and carbon ball dispersion liquid is 3:1 ~ 4:1.
Through field emission scanning electron microscope, infrared spectrum the structure of the Graphene/carbon ball composite material of the present invention's preparation is described below.
Fig. 1 is field emission scanning electron microscope (SEM) picture of Graphene of the present invention.As can beappreciated from fig. 1, Graphene presents the tulle shape that curls and twine.Fig. 2 is field emission scanning electron microscope (SEM) picture of the carbon ball of the present invention's preparation.As can beappreciated from fig. 2, the carbon ball is the bead of uniform size that diameter is about 220nm.Fig. 3 is field emission scanning electron microscope (SEM) picture of Graphene of the present invention/carbon ball composite material; As can beappreciated from fig. 3; The overall structure of Graphene/carbon ball composite material is a stratiform; Be embodied between the graphene layer of tulle shape and be mingled with the carbon ball, be convenient to Graphene and show good electric double layer capacitance thereby the carbon ball has effectively hindered the reunion of Graphene therein and contact the passage that provides favourable for electrolyte ion and Graphene are surperficial; Moreover under the effect of Graphene, carbon ball nano particle well disperses, and also helps it and is the certain electric capacity of composite material contribution.
Fig. 4 is the infrared spectrum of Graphene of the present invention/carbon ball composite material, Graphene and carbon ball.As can beappreciated from fig. 4 Graphene is at 1572 cm
– 1There is a strong absworption peak at the place, and it is owing to the skeletal vibration of sp2 hydridization carbon atomic layer, and other oxygen-containing functional group of relevant graphene oxide absworption peak disappear and explain and successfully reduced for Graphene through the reflux oxidation Graphene; In conjunction with the infrared spectrum of Graphene, carbon ball, Graphene and carbon ball are effectively compound in discovery Graphene/carbon ball composite material, and this is consistent with the result that its field emission scanning electron microscope obtains.
(2) preparation of electrode of super capacitor and electrochemical property test
Pulverize last and acetylene black, electrically conductive graphite, polytetrafluoroethylene of the Graphene/carbon ball composite material of above-mentioned preparation mixed with the mass ratio of 75:10:10:5, be modulated into mud with absolute ethyl alcohol; Mud spread upon (amount that mud spreads upon on the nickel foam collector is 2 ~ 2.5mg/cm on the nickel foam collector
2), after the drying, it is pressed into the sheet that thickness is 0.2 ~ 0.3mm, and (the pressure size is 7 * 10
5~ 8 * 10
5Pa, the retention time is 4s ~ 6s), promptly get electrode of super capacitor.
With the Graphene/carbon ball composite electrode of above-mentioned preparation as work electrode, with platinum guaze for being that reference electrode is formed three-electrode system and carried out electrochemical property test (and compare with Graphene, carbon ball electrode) to electrode, with Hg/HgO.
Fig. 5 is Graphene of the present invention/carbon ball composite electrode and Graphene, the carbon ball electrode cyclic voltammogram (potential window-0.9 V is to 0.1 V) when sweep speed is 20mV/s in the KOH of 6 mol/L electrolyte.The result of Fig. 5 shows that than composite material and Graphene, the area of the cyclic voltammetry curve of carbon ball is very little, explains that simple carbon ball electrode is very littler than electric capacity; The cyclic voltammetry curve shape of composite material and Graphene approaches rectangle; Explain that they have all shown electric double layer capacitance in electrochemical reaction process; But the curve shape of composite material does not have the rule of Graphene, and its reason is that the carbon ball in the composite material also participated in electrochemical reaction; Comparatively speaking, the cyclic voltammetry curve area of composite material is bigger than Graphene and carbon ball, explains that Graphene/carbon ball composite electrode can provide bigger ratio electric capacity than Graphene and carbon ball electrode.
Under the ratio electric current of 1A/g, it is carried out charge-discharge test (and compare with Graphene, carbon ball electrode).Fig. 6 is the charge and discharge electrograph of 1A/g than electric current for Graphene of the present invention/carbon ball composite electrode and Graphene, carbon ball electrode in the KOH of 6 mol/L electrolyte.Fig. 6 result displayed shows that three's charging and discharging curve all approaches straight line, explains that they all show the characteristic of electric double layer capacitance in electrochemical reaction process; And the ratio electric capacity of Graphene/carbon ball composite electrode is greater than the ratio electric capacity of simple Graphene and carbon ball electrode.
Fig. 7 is that Graphene of the present invention/carbon ball composite material and Graphene electrodes initial voltage in the KOH of 6 mol/L electrolyte are-0.2V that frequency range is 0.01 ~ 10
5The AC impedance figure of Hz; Fig. 8 is the AC impedance figure of carbon ball electrode under the same terms.Fig. 7 result displayed shows that at high frequency region, the simple Graphene electrodes of electric charge mass transfer resistance ratio of Graphene/carbon ball composite electrode is little; At low frequency range, composite material and Graphene show the characteristics of electric double layer capacitance.Fig. 8 shows that carbon ball electrode shows as the characteristics of diffusion control at low frequency range.AC impedance figure shows that Graphene/carbon ball composite material can be used as good electrode material for super capacitor.
Cycle life figure when Fig. 9 is 2A/g than electric current for the electrode of super capacitor of the present invention preparation in 6 mol/LKOH electrolyte.Figure 10 is the part charging and discharging curve of intercepting in the cycle life test process.Fig. 9,10 explanation Graphene/carbon ball composite electrodes have shown good cyclical stability.
In sum, the composite material of the present invention's preparation has high electrochemical performance, and it has good ratio electric capacity as electrode material for super capacitor, and cycle life is stable.
The present invention is relative, and prior art has the following advantages:
1, the present invention obtains Graphene/carbon ball composite material through graphene oxide and self assembly under certain conditions of carbon ball and reduction, and its constituent Graphene and carbon ball are material with carbon element; Have with low cost; Wide material sources, light weight, renewable; Characteristics such as pollution-free meet business-like basic demand as electrode material for super capacitor.
2, Graphene of the present invention derives from the reduction of graphite oxide, and the reduction through hydrazine hydrate makes Graphene effectively recover its structure, has guaranteed the quick transmission of its electric charge in electrochemical reaction process.
3, the present invention makes composite material in electrochemical reaction process, contribute remarkable ratio electric capacity through carbon ball and the compound reunion that effectively reduces Graphene of Graphene.
Description of drawings
Fig. 1 is field emission scanning electron microscope (SEM) picture of Graphene of the present invention.
Fig. 2 is field emission scanning electron microscope (SEM) picture of carbon ball of the present invention.
Fig. 3 is field emission scanning electron microscope (SEM) picture of Graphene of the present invention/carbon ball composite material.
Fig. 4 is the infrared spectrum of Graphene of the present invention/carbon ball composite material, Graphene and carbon ball.
Fig. 5 is Graphene of the present invention/carbon ball composite electrode and Graphene, the carbon ball electrode cyclic voltammogram when sweep speed is 20mV/s in 6 mol/LKOH electrolyte.
Fig. 6 is the charge and discharge electrograph of 1A/g than electric current for Graphene of the present invention/carbon ball composite electrode and Graphene, carbon ball electrode in 6 mol/LKOH electrolyte.
Fig. 7 is that Graphene of the present invention/carbon ball composite material and Graphene electrodes initial voltage in 6 mol/LKOH electrolyte are-0.2V that frequency range is 0.01-10
5The AC impedance figure of Hz.
Fig. 8 is carbon ball electrode AC impedance figure in 6 mol/LKOH electrolyte and under the same conditions.
Fig. 9 is the cycle life figure of 2A/g than electric current for the electrode of super capacitor of the present invention preparation in 6 mol/LKOH electrolyte.
Figure 10 is the part charging and discharging curve of intercepting in the cycle life test process.
Embodiment
Do further detailed explanation below in conjunction with the accompanying drawing specific embodiments of the invention.
The instrument and the reagent that use:
CHI660B electrochemical workstation (Shanghai occasion China instrument company) is used for electrochemical property test; Blue electricity (LAND) series battery test macro (the blue electric Electronics Co., Ltd. in Wuhan) is used for the cycle life test of electrode; Electronic balance (Beijing Sai Duolisi Instr Ltd.) is used for the weighing medicine; The pattern that JSM-6701F awkward silence at a meeting emission type ESEM (Jeol Ltd.) is used for material characterizes; FTS3000 type Fourier infrared spectrograph (U.S. DIGILAB company) is used for analytic sample and forms.Glucose (extraordinary chemical reagent development centre, North China); Pintsch process graphite powder, acetylene black, electrically conductive graphite (Guiyang, Hunan Province Tan Sha graphite factory), sodium nitrate (Xi'an chemical reagent factory), wealthy family's acid potassium (Tianjin section close europeanized reagent development centre); Hydrogen peroxide solution (going up chemical reagent Co., Ltd of the marine Qin); Hydrazine hydrate (85%, go up chemical reagent Co., Ltd of the marine Qin), absolute ethyl alcohol (Anhui An Te biochemistry corporation,Ltd.); Toluene (North China sales branch of China Petrochemical Industry), potassium hydroxide (Red Star chemical plant, Beijing).Nickel foam collector (the many reforms in Shanghai Materials Co., Ltd).
That uses in the experimentation is first water, test used reagent be analyze pure.
Embodiment 1:
(1) preparation of composite material
(1) preparation of graphite oxide: get the 92ml mass fraction and be 98% the concentrated sulfuric acid in the beaker of 1000ml, ice-water bath is reduced to below 4 ℃ temperature, and strong agitation also adds the Pintsch process graphite powder of 4g simultaneously; Treat that it behind strong agitation 0.5h, adds the potassium permanganate of 3g sodium nitrate and 12g successively in ice-water bath; Behind the strong agitation reaction 1h, take out beaker in the ice-water bath, be allowed to condition under the normal temperature and add 300ml distilled water slowly behind the strong agitation reaction 3h; Treat to add 500ml distilled water once more after the room temperature of its recovery, add the 50ml mass fraction behind the 10min and be 30% hydrogen peroxide; After leaving standstill 24h, with the products therefrom suction filtration, the use mass fraction is 5% hydrochloric acid solution washing earlier, repeatedly washs to filtrating with distilled water and does not have SO
4 2-Exist and be neutrality; At 60 ℃ of vacuumize 18h, grind into powder promptly gets graphite oxide with the suction filtration product.
(2) preparation graphene oxide presoma dispersion liquid: take by weighing graphite oxide 0.12g; Under strong agitation, join in the distilled water of 400ml; Using 10% ammoniacal liquor accent pH is 9～10, with its at room temperature ultrasonic 1h, obtains the graphene oxide presoma dispersion liquid of 0.3mg/ml.
(3) carbon ball preparation: get 14.4g glucose and be dissolved in the 160ml distilled water, glucose solution is transferred in the autoclave of 200ml that inner bag is a polytetrafluoroethylene, at 180 ℃ of following hydrothermal treatment consists 4h.With the hydrothermal product suction filtration, and repeatedly with ethanol and distilled water washing.After treating that washing finishes, product at 60 ℃ of following vacuumize 12h, is promptly obtained the carbon ball.
(4) preparation carbon ball dispersion liquid: take by weighing carbon ball 10mg, in the last 100ml of the joining distilled water of pulverizing, using 10% ammoniacal liquor accent pH is 9 ~ 10, be not higher than 10 ℃ of ultrasonic dispersion 1h down, promptly obtains the carbon ball dispersion liquid of 0.1 mg/ml.
(5) preparation of Graphene/carbon ball composite material: the hydrazine hydrate that in the graphene oxide presoma dispersion liquid that step (2) obtains, adds 2ml; Add the carbon ball dispersion liquid that step (4) obtains under the strong agitation again; After mixing, add 50ml toluene, at 90 ℃ of refluxed 7h; After removing toluene products therefrom is filtered, and repeatedly wash with distilled water and ethanol, 60 ℃ of following vacuumize 12h obtain Graphene/carbon ball composite material.
(2) preparation of electrode of super capacitor and electrochemical property test
(1) preparation of electrode: with Graphene/carbon ball composite material pulverize in agate mortar of above-mentioned preparation, get 75mg and with acetylene black 10mg, electrically conductive graphite 10mg, polytetrafluoroethylene 5mg mixes.Add a spot of absolute ethyl alcohol, mixture is processed mud.Mud is spread upon on the nickel foam collector, and its area size is 1cm
2Under 60 ℃ in vacuum, be dried 24h subsequently.The nickel foam collector that scribbles electroactive material that drying is good is pressed into the thick thin slice of 0.2mm on tablet press machine (pressure is 8 * 10
5Pa, the retention time is 4s).
(2) electrochemical property test of electrode
Test than electric capacity: with the Graphene/carbon ball composite electrode of above-mentioned preparation is work electrode, platinum guaze for being that reference electrode is formed three-electrode system and carried out electrochemical property test to electrode, Hg/HgO electrode; Electrolyte is 6 mol/LKOH solution, potential window-0.9 V ~ 0.1 V.Carry out the cyclic voltammetry scan (see figure 5) during for 20mV/s in sweep speed.The ratio electric current that with the size is 1A/g carries out the charge-discharge test (see figure 6) to it, and the ratio electric capacity that records Graphene/carbon ball composite electrode is 200F/g.Be-0.2V that frequency range is 0.01 ~ 10 with initial voltage
5Hz carries out the ac impedance measurement (see figure 7) to it: at high frequency region, the AC impedance figure of Graphene/carbon ball composite material is slightly less than Graphene, and the simple Graphene electrodes of electric charge mass transfer resistance ratio little of composite electrode is described; At low frequency range, composite material and Graphene show the characteristics of electric double layer capacitance.
The cycle life test: the Graphene/carbon ball composite electrode with above-mentioned preparation is that work electrode, platinum guaze are for being reference electrode composition three-electrode system to electrode, Hg/HgO electrode; In the LAND test macro, carry out the cycle life test; Electrolyte is 6 mol/LKOH solution, potential window-0.9 V ~ 0.1 V.Graphene/2000 constant current charge-discharge circulations of carbon ball composite electrode experience back still keeps initial than 99% of electric capacity than electric capacity.
(1) preparation of composite material
(1) preparation of graphite oxide: with embodiment 1.
(2) preparation graphene oxide presoma dispersion liquid: take by weighing graphite oxide 0.08g; Under strong agitation, join in the distilled water of 400ml; Using 10% ammoniacal liquor accent pH is 9～10, with its at room temperature ultrasonic 1h, obtains the graphene oxide presoma dispersion liquid of 0.2mg/ml.
(3) carbon ball preparation: get 11.52g glucose and be dissolved in the 160ml distilled water, glucose solution is transferred in the autoclave of 200ml that inner bag is a polytetrafluoroethylene, at 180 ℃ of following hydrothermal treatment consists 7h.With the hydrothermal product suction filtration, and repeatedly with ethanol and distilled water washing.After treating that washing finishes, product at 60 ℃ of following vacuumize 12h, is promptly obtained the carbon ball.
(4) preparation carbon ball dispersion liquid: take by weighing carbon ball 15mg, in the last 100ml of the joining distilled water of pulverizing, using 10% ammoniacal liquor accent pH is 9 ~ 10, be not higher than 10 ℃ of ultrasonic dispersion 1h down, promptly obtains the carbon ball dispersion liquid of 0.15 mg/ml.
(5) preparation of Graphene/carbon ball composite material: in the graphene oxide presoma dispersion liquid that step (2) obtains, add the hydrazine hydrate of 2ml, under strong agitation, add the carbon ball dispersion liquid that step (4) obtains; After mixing, will add 40ml toluene, and at 80 ℃ of refluxed 7h; After removing toluene products therefrom is filtered, and repeatedly wash with distilled water and ethanol, 60 ℃ of following vacuumize 12h obtain Graphene/carbon ball composite material.
(2) preparation of electrode of super capacitor and electrochemical property test
(1) preparation of electrode: with the Graphene/carbon ball composite material of above-mentioned preparation at the agate mortar pulverize, get 75mg and with acetylene black 10mg, electrically conductive graphite 10mg, polytetrafluoroethylene 5mg mixes.Add a spot of absolute ethyl alcohol, mixture is processed mud.Mud is spread upon on the nickel foam collector, and its area size is 1cm
2, under 60 ℃ in vacuum, be dried 24h subsequently.The nickel foam collector that scribbles electroactive material that drying is good is pressed into the thick thin slice of 0.2mm on tablet press machine (pressure is 8 * 10
5Pa, the retention time is 5s).
(2) electrochemical property test of electrode
Test than electric capacity: with the Graphene/carbon ball composite electrode of above-mentioned preparation is work electrode, platinum guaze for being that reference electrode is formed three-electrode system and carried out electrochemical property test to electrode, Hg/HgO electrode; Electrolyte is 6 mol/L KOH solution, potential window-0.9 V ~ 0.1 V.Carry out cyclic voltammetry scan during for 20mV/s in sweep speed.The ratio electric current that with the size is 1A/g carries out charge-discharge test to it, and the ratio electric capacity that records Graphene/carbon ball composite electrode is 183F/g.Be-0.2V that frequency range is 0.01 ~ 10 with initial voltage
5Hz carries out ac impedance measurement to it: test result is with embodiment 1.
The cycle life test: the Graphene/carbon ball composite electrode with above-mentioned preparation is that work electrode, platinum guaze are for being reference electrode composition three-electrode system to electrode, Hg/HgO electrode; Carry out the cycle life test at the LAND test macro; Electrolyte is 6 mol/LKOH solution, potential window-0.9 V ~ 0.1 V.Test result: Graphene/2000 constant current charge-discharge circulations of carbon ball composite electrode experience back still so keeps initial than 98.6% of electric capacity than electric capacity.
(1) preparation of composite material
(1) preparation of graphite oxide: with embodiment 1.
(2) preparation graphene oxide presoma dispersion liquid: take by weighing graphite oxide 0.12g; Under strong agitation, join in the distilled water of 300ml; Using 10% ammoniacal liquor accent pH is 9～10, with its at room temperature ultrasonic 1h, obtains the graphene oxide presoma dispersion liquid of 0.4mg/ml.
(3) carbon ball preparation: take by weighing in the dissolving of 10.176g glucose and the 160ml distilled water, glucose solution is transferred in the autoclave of 200ml that inner bag is a polytetrafluoroethylene, at 170 ℃ of following hydrothermal treatment consists 5h.With the hydrothermal product suction filtration, and repeatedly with ethanol and distilled water washing.After treating that washing finishes, product at 60 ℃ of following vacuumize 12h, is promptly obtained the carbon ball.
(4) preparation carbon ball dispersion liquid: take by weighing carbon ball 20mg, last the joining in the distilled water of pulverizing, using 10% ammoniacal liquor accent pH is 9 ~ 10, be not higher than 10 ℃ of ultrasonic dispersion 1h down, promptly obtains the carbon ball dispersion liquid of 0.2 mg/ml.
(5) preparation of Graphene/carbon ball composite material: in the graphene oxide presoma dispersion liquid that step (2) obtains, add the hydrazine hydrate of 3ml, under strong agitation, add the carbon ball dispersion liquid that step (4) obtains; After mixing, add 35ml toluene, and at 90 ℃ of refluxed 5h; After removing toluene products therefrom is filtered, and repeatedly wash with distilled water and ethanol, 60 ℃ of following vacuumize 12h obtain Graphene/carbon ball composite material.
(2) preparation of electrode of super capacitor and electrochemical property test
(1) preparation of electrode: with the Graphene/carbon ball composite material of above-mentioned preparation at the agate mortar pulverize, get 75mg and with acetylene black 10mg, electrically conductive graphite 10mg, polytetrafluoroethylene 5mg mixes.Add a spot of absolute ethyl alcohol, mixture is processed mud.Mud is spread upon on the nickel foam collector, and its area size is 1 cm
2, under 60 ℃ in vacuum, be dried 24h subsequently.The nickel foam collector that scribbles electroactive material that drying is good is pressed into the thick thin slice of 0.3mm on tablet press machine (pressure is 7 * 10
5Pa, the retention time is 6s).
(2) electrochemical property test of electrode
Test than electric capacity: with the Graphene/carbon ball composite electrode of above-mentioned preparation is work electrode, platinum guaze for being that reference electrode is formed three-electrode system and carried out electrochemical property test to electrode, Hg/HgO electrode; Electrolyte is 6 mol/LKOH solution, potential window-0.9 V ~ 0.1 V.Carry out cyclic voltammetry scan during for 20mV/s in sweep speed.The ratio electric current that with the size is 1A/g carries out charge-discharge test to it, and the ratio electric capacity that records Graphene/carbon ball composite electrode is 176F/g.Be-0.2V that frequency range is 0.01-10 with initial voltage
5Hz carries out ac impedance measurement to it: test result is with embodiment 1.
The cycle life test: the Graphene/carbon ball composite electrode with above-mentioned preparation is that work electrode, platinum guaze are for being reference electrode composition three-electrode system to electrode, Hg/HgO electrode; In the LAND test macro, carry out the cycle life test; Electrolyte is 6 mol/L KOH solution, potential window-0.9 V ~ 0.1 V.Graphene/2000 constant current charge-discharge circulations of carbon ball composite electrode experience back still so keeps initial than 98.9% of electric capacity than electric capacity.
Claims (6)
1. the preparation method of Graphene/carbon ball composite material comprises following processing step
(1) preparation of graphene oxide presoma dispersion liquid: be scattered in the distilled water graphite oxide is ultrasonic, form the graphene oxide presoma dispersion liquid of concentration 0.2 ~ 0.4mg/ml;
(2) preparation of carbon ball: glucose is dissolved in the distilled water, and forming concentration is the glucose solution of 0.4 ~ 0.6mol/L, glucose solution is moved in the autoclave, in 160 ~ 180 ℃ of following hydrothermal treatment consists 4 ~ 7h again; Suction filtration, with ethanol, distilled water cyclic washing, drying obtains the carbon ball;
(3) preparation of carbon ball dispersion liquid: with above-mentioned carbon ball last ultrasonic being scattered in the distilled water of pulverizing, forming concentration is the carbon ball dispersion liquid of 0.1 ~ 0.2mg/ml;
(4) preparation of Graphene/carbon ball composite material: in above-mentioned graphene oxide presoma dispersion liquid, add hydrazine hydrate earlier, add carbon ball dispersion liquid under the strong agitation again, mix the back and transfer pH=9 ~ 10; The toluene that adds mixed system volume 7 ~ 10% is in 80 ~ 90 ℃ of 5 ~ 7h that reflux; After removing toluene products therefrom is filtered, with distilled water and ethanol cyclic washing, drying obtains Graphene/carbon ball composite material;
The addition of hydrazine hydrate is in the said graphene oxide presoma dispersion liquid: the volume ratio of graphite oxide quality and hydrazine hydrate is 100mg:1.5ml ~ 100mg:3ml, and the volume ratio of said graphene oxide presoma dispersion liquid and carbon ball dispersion liquid is 3:1 ~ 4:1.
2. Graphene/carbon ball the composite material of method preparation according to claim 1.
3. like the application of the said Graphene of claim 2/carbon ball composite material in making electrode of super capacitor.
4. like the application of the said Graphene of claim 3/carbon ball composite material in making electrode of super capacitor; It is characterized in that: pulverize last and acetylene black, electrically conductive graphite, polytetrafluoroethylene of Graphene/carbon ball composite material mixed with the mass ratio of 75:10:10:5, be modulated into mud with absolute ethyl alcohol; Mud is spread upon on the nickel foam collector, after the drying, it is pressed into the sheet that thickness is 0.2 ~ 0.3mm, promptly get electrode of super capacitor.
5. like the application of the said Graphene of claim 4/carbon ball composite material in making electrode of super capacitor, it is characterized in that: the amount that said mud spreads upon on the nickel foam collector is 2 ~ 2.5mg/cm
2
Like the Graphene/carbon ball composite material of the said method of claim 4 preparation in the application of making electrode of super capacitor, it is characterized in that: said compressing tablet is to be 7 * 10 at pressure
5~ 8 * 10
5The following retention time of Pa is 4 ~ 6s.
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| CN103811184A (en) * | 2012-11-15 | 2014-05-21 | 海洋王照明科技股份有限公司 | Graphene-carbon nano tube combined electrode and super capacitor manufacturing method |
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| CN107959017A (en) * | 2017-12-24 | 2018-04-24 | 株洲市智汇知识产权运营服务有限责任公司 | A kind of solid carbon ball lithium ion battery negative material of graphene/oxide coated by zinc and preparation method thereof |
| CN108183208A (en) * | 2017-12-24 | 2018-06-19 | 林荣铨 | A kind of graphene/solid carbon ball lithium ion battery negative material preparation method and preparation method thereof |
| CN114335544A (en) * | 2022-01-05 | 2022-04-12 | 湖南大晶新材料有限公司 | Water-based binder, lithium ion battery cathode material and lithium ion battery |
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| CN116463524A (en) * | 2023-04-04 | 2023-07-21 | 东莞市金庆新材料有限公司 | Preparation method of high-thermal-conductivity composite material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009094277A2 (en) * | 2008-01-14 | 2009-07-30 | The Regents Of The University Of California | High-throughput solution processing of large scale graphene and device applications |
| CN102044666A (en) * | 2010-11-19 | 2011-05-04 | 杭州电子科技大学 | Method for preparing lithium iron phosphate composite material for lithium cells |
| US20110104553A1 (en) * | 2009-10-29 | 2011-05-05 | Uchicago Argonne, Llc | Autogenic pressure reactions for battery materials manufacture |
| US20110111303A1 (en) * | 2009-11-06 | 2011-05-12 | Northwestern University | Electrode material comprising graphene composite materials in a graphite network formed from reconstituted graphene sheets |
-
2011
- 2011-11-29 CN CN 201110386968 patent/CN102509643B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009094277A2 (en) * | 2008-01-14 | 2009-07-30 | The Regents Of The University Of California | High-throughput solution processing of large scale graphene and device applications |
| US20110104553A1 (en) * | 2009-10-29 | 2011-05-05 | Uchicago Argonne, Llc | Autogenic pressure reactions for battery materials manufacture |
| US20110111303A1 (en) * | 2009-11-06 | 2011-05-12 | Northwestern University | Electrode material comprising graphene composite materials in a graphite network formed from reconstituted graphene sheets |
| CN102044666A (en) * | 2010-11-19 | 2011-05-04 | 杭州电子科技大学 | Method for preparing lithium iron phosphate composite material for lithium cells |
Non-Patent Citations (3)
| Title |
|---|
| 《无机材料学报》 20091130 刘守新等 水热法制备炭球--活性炭复合材料 第24卷, 第6期 * |
| 刘守新等: "水热法制备炭球——活性炭复合材料", 《无机材料学报》, vol. 24, no. 6, 30 November 2009 (2009-11-30) * |
| 程立强等: "球形碳材料的研究进展", 《化学进展》, vol. 18, no. 10, 31 October 2006 (2006-10-31) * |
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