CN102324505A - Preparation method of graphene loaded with anatase type nano titanium dioxide and application thereof - Google Patents
Preparation method of graphene loaded with anatase type nano titanium dioxide and application thereof Download PDFInfo
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- CN102324505A CN102324505A CN201110211177A CN201110211177A CN102324505A CN 102324505 A CN102324505 A CN 102324505A CN 201110211177 A CN201110211177 A CN 201110211177A CN 201110211177 A CN201110211177 A CN 201110211177A CN 102324505 A CN102324505 A CN 102324505A
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Abstract
The invention discloses a preparation method of graphene loaded with anatase type nano titanium dioxide and an application thereof. The preparation method comprises the following steps: preparing graphite oxide from crystalline flake graphite; carrying out reduction reaction on the graphite oxide to obtain graphene by taking hydrazine hydrate as a reducing agent and sodium dodecyl benzene sulfonate as a dispersing agent; preparing titanium hydroxide colloidal solution by taking tetrabutyl titanate as a titanium source; mixing the ethanol solution of graphene and the titanium hydroxide colloidal solution, stirring and calcining to prepare the graphene loaded with anatase type nano titanium dioxide. The graphene loaded with anatase type nano titanium dioxide prepared by the method can be mixed with copper powder to prepare the negative electrode of a nickel-hydride secondary battery. The method provided by the invention has the advantages of simple preparation process and low cost and is easy to operate. When the prepared graphene loaded with anatase type nano titanium dioxide is used as the active material of the cathode of the secondary battery, the effects of high discharge specific capacity and good circulation stability are achieved.
Description
Technical field
The present invention relates to a kind of preparation method of graphene and application thereof of load anatase titanium dioxide, belong to field of electrochemical power source.
Background technology
Graphene is the two-dimentional carbon atom crystal of finding in recent years, is a kind of single or multiple lift graphite material as thin as a wafer, and it is one of carbon current material and Condensed Matter Physics hot research fields.Graphene is to construct zero dimension fullerene, one dimension CNT, said three-dimensional body phase graphite Sp
2The basic system unit of hydridization carbon.Graphene has a lot of peculiar character.Graphene is a kind of material that does not have energy gap, shows metallicity; In the Graphene of individual layer, each carbon atom all has the not electronics of Cheng Jian, therefore has extraordinary conductivity; Hole and electronics in the Graphene are separated from each other, and have caused the generation of new electrical conductivity phenomenon, for example irregular quantum hall effect.Graphene has boundless application prospect; Its peculiar character provides good Physical Experiment platform still to make nano electron device---high frequency transistor with but the optimal material of electron transistor is also having very wide application prospect aspect micro-filter screen and the superconduction.In addition, Graphene also shows good electro-chemical activity, is the energy storage material of excellent performance, has huge application space as the negative material of Ni-MH battery.
Titanium dioxide is a kind of high yield, low cost, eco-friendly material; In the charge discharge process, titanium dioxide can keep stable structure, and anatase-type nanometer titanium dioxide has good photocatalytic effect.Because nanostructure and conductive coating effect, titanium dioxide is with a wide range of applications in large-scale energy storage research.
Relevant bibliographical information [Self-Assembled TiO2-Graphene Hybrid Nanostructures for Enhanced Li-Ion Insertion]; Adopt self-assembling method to prepare the graphene composite material of nano titanium oxide load; Be used for the lithium ion battery Study on Efficiency, the Graphene that adopts in the document is rapid intensification expansion gained, gained graphene suspension poor stability; Be unfavorable for that nano titanium oxide evenly disperses on the Graphene lamella; For the purpose that reaches dispersion and adopt the anion sulfate acid surfactant that the aqueous solution of Graphene is carried out stabilisation, improved preparation cost, contaminated environment.
Summary of the invention
The object of the invention is to provide a kind of preparation method of graphene and application thereof of load anatase-type nanometer titanium dioxide; Described preparation method's process is simple, and the Graphene of made load anatase titanium dioxide has high electrochemistry capacitance as the nickel-hydrogen secondary battery negative electrode material.
The present invention realizes that through following technical scheme a kind of preparation method of graphene of load anatase-type nanometer titanium dioxide is characterized in that comprising following process:
(1) preparation graphite oxide: by the H of every gram natural flake graphite with mass concentration 98%
2SO
4Ratio for 30-40ml joins H with natural flake graphite
2SO
4In, under in ice-water bath, stirring, be 5: 1 by the mass ratio of potassium permanganate and natural flake graphite, add KMnO again
4, reaction 0.5-2h, then; Mixture transferred in temperature 30-40 ℃ the water-bath, continue to stir 30～60min, be warming up to temperature 50-70 ℃ again; Stir 0.5-2h, with deionized water 80-120mL, with the hydrogen peroxide solution 10-20mL ratio of mass concentration 30%, continue to stir down in every gram natural flake graphite; Add deionized water and hydrogen peroxide solution reaction 10-20min successively; Product is through centrifugation, and filter cake is used hydrochloric acid and deionized water wash to the sulfate radical-free ion of mass concentration 2-10% successively, in vacuum drying chamber, obtains graphite oxide in temperature 50-80 ℃ of dry 24-48h again;
(2) preparation Graphene: the graphite oxide of step (1) system is dispersed in compound concentration 0.5-1mg/ml solution in the deionized water, and the ultrasonic 2-5h that peels off obtains graphene oxide solution; In graphene oxide solution, add neopelex; The quality of neopelex and the mass ratio of graphite oxide are 1: (1-3); In graphene oxide solution, add mass concentration again and be 85% hydrazine hydrate; The volumetric usage of this hydrazine hydrate solution is by every gram graphite oxide 1-10ml, behind temperature 70-80 ℃ of water-bath backflow 24-48h, product use deionized water wash to pH be 7; The Graphene that obtains is joined in the absolute ethyl alcohol, be made into the ethanolic solution that concentration is the Graphene of 0.5-1mg/ml;
(3) preparation titanium hydroxide colloidal solution: butyl titanate splashed into to be mixed with volumetric concentration in the absolute ethyl alcohol be that the solution of 1-3% is end liquid; Under agitation in end liquid, drip mixed liquor; Described mixed liquor is that 36.5% hydrochloric acid, absolute ethyl alcohol and deionized water are by volume measured 3～4 times, 1.5～1.8 times and 1.5～1.8 times of being respectively the butyl titanate volume and formed by mass concentration, obtains titanium hydroxide colloidal solution after mixed liquor dropwises;
The ethanolic solution of the Graphene that (4) step (2) is made and the titanium hydroxide colloidal solution that step (3) makes is (10-50) by volume: 1 mixed; Stir 30min-60min; Leave standstill behind the 12-24h in drying box in 60 ℃ of-80 ℃ of evaporates to dryness of temperature; With putting into tube furnace after the powder grinding that obtains, with the flow feeding argon gas of 100ml/min, in argon gas atmosphere; Heating rate by 10 ℃/min is warming up to 300 ℃-500 ℃ calcinings of temperature 2h-3h, obtains the Graphene of load anatase-type nanometer titanium dioxide.
With the application of the Graphene of the prepared load anatase-type nanometer titanium dioxide of said method, the negative pole of the Graphene of this load anatase-type nanometer titanium dioxide and the mixed nickel-hydrogen secondary cell of copper powder.
The present invention has the following advantages: the preparation method of graphene of load anatase-type nanometer titanium dioxide of the present invention, and process is simple, and easy operating, and cost is low.The titanium dioxide granule size of load is little and be uniformly dispersed.With the Graphene of the prepared load anatase-type nanometer titanium dioxide active material as nickel-hydrogen secondary battery negative electrode, specific discharge capacity is high, and good cycling stability.
Description of drawings
Fig. 1 is the SEM photo of the embodiment of the invention 1 prepared Graphene.
Fig. 2 is the TEM photo of the embodiment of the invention 1 prepared Graphene.
Fig. 3 is the TEM photo of the Graphene of the embodiment of the invention 1 prepared load anatase-type nanometer titanium dioxide.
The XRD spectra of the Graphene of the load anatase-type nanometer titanium dioxide that Fig. 4 makes for the inventive method.Wherein (a) is the XRD spectra of Graphene of the load anatase-type nanometer titanium dioxide of the said method preparation of embodiment 1; (b) be the XRD spectra of Graphene of the load anatase-type nanometer titanium dioxide of the said methods preparation of embodiment 2; (c) be the XRD spectra of Graphene of the load anatase-type nanometer titanium dioxide of the said methods preparation of embodiment 3.
Fig. 5 is the charging and discharging curve of the Graphene of the embodiment of the invention 1 prepared load anatase-type nanometer titanium dioxide as the nickel-hydrogen secondary cell of negative material.
Fig. 6 is the stable circulation linearity curve of the Graphene of the embodiment of the invention 1 prepared load anatase-type nanometer titanium dioxide as the nickel-hydrogen secondary cell of negative material.
Embodiment
Embodiment 1
In the 120ml mass concentration is to add the 3g natural flake graphite in 98% the sulfuric acid, with mixture in ice-water bath slowly to add 15g potassium permanganate in the speed whipping process of 200rpm; Behind the ice bath 2h, mixture is transferred in 35 ℃ of water-baths of temperature, continued to stir 1h; 65 ℃ of warming-in-water to temperature are stirred 2h, stir simultaneously, slowly add the 250ml deionized water, add deionized water again to 1400ml, add the 30ml mass concentration again and be 30% hydrogen peroxide solution, reaction 20min at the gained mixed liquor.It is that 5% watery hydrochloric acid carries out centrifuge washing that products therefrom is used mass concentration, and washing is to there not being SO
4 2-(use BaCl
2Check), the washings that obtains in 60 ℃ of dryings of temperature, obtains graphite oxide in vacuum drying chamber.
Get the 100mg graphite oxide that above-mentioned steps makes and be dispersed in the 100ml deionized water, the ultrasonic 2h that peels off, obtaining concentration is the graphene oxide solution of 1mg/ml.In graphene oxide solution, add the 100mg neopelex; Add the 0.1ml mass concentration again and be 85% hydrazine hydrate; With mixed liquor at 80 ℃ of refluxed reductase 12s of temperature 4h; Use the 500ml deionized water wash then, obtain Graphene, the gained Graphene is joined ultrasonic dispersion in the 100ml absolute ethyl alcohol obtain behind the ethanolic solution of Graphene for use.
The 1.5ml butyl titanate is splashed in the 50ml absolute ethyl alcohol as end liquid; The 5ml mass concentration is that the mixed liquor of 36.5% hydrochloric acid, 2.5ml absolute ethyl alcohol and 2.5ml deionized water is as titrating solution; At rotating speed is under 300rpm stirs; Titrating solution slowly is added drop-wise in the end liquid, obtains titanium hydroxide colloidal solution behind the dropping 20min, get gained titanium hydroxide colloidal solution 10ml; Join in the 100ml ethanolic solution of graphitiferous alkene of gained in the above-mentioned steps, the 200rpm rotating speed stirs down behind the 0.5h in drying box in 60 ℃ of dryings of temperature.After the product that obtains pulverized, in tube furnace, feed argon gas with the flow of 100ml/min, the argon gas atmosphere protection is calcined 2h after being warming up to 500 ℃ of temperature with the heating rate of 10 ℃/min down, obtains the Graphene of load nano-titanium dioxide.
Add in people's mould after the Graphene composite powder of 20mg load anatase-type nanometer titanium dioxide and 180mg copper powder mixed; One deck nickel foam all is housed up and down; Take out behind 400MPa pressure pressed 5min with powder compressing machine, obtain columned cathode sheets, behind the welding lead; To there be a side of solder joint to seal admittedly, obtain work electrode with epoxy resin.As to electrode, Hg/HgO is a reference electrode with the high power capacity sintered nickel electrode. electrolyte is 6molL
-1KOH solution.Adopt three-electrode system, carry out the electrochemical hydrogen storage performance test under the atmospheric pressure at room, charging and discharging currents is 20mA, and the discharge stopping potential is 0V (VS.Hg/HgO), and 100 cycles circulate.Fig. 5 is the charging and discharging curve of the graphene-supported composite titania material that adopts the inventive method and make, and discharge capacity reaches 1194.2mAh/g first, discharge and recharge 66 circulations after discharge capacity reach maximum, be 1982.5mAh/g.Fig. 6 is the cyclical stability figure of the graphene-supported composite titania material that adopts the inventive method and make, visible its good cycling stability, and after 100 circulations, specific discharge capacity is not less than 1600.4mAh/g.
Embodiment 2
The process of Graphene that present embodiment prepares the load anatase-type nanometer titanium dioxide is identical with the process of embodiment 1; Different is: calcining heat changes 400 ℃ of temperature into by 500 ℃ of the temperature among the embodiment 1; Calcine 2h, obtain the Graphene of nano titanium oxide load.Shown in Fig. 4 (b), can find out that by figure the anatase crystal of nano titanium oxide is lower than degree of crystallinity among the embodiment 1 by the XRD spectra of the Graphene of the made nano titanium oxide load of present embodiment.
Embodiment 3
The process of Graphene that present embodiment prepares the load anatase-type nanometer titanium dioxide is identical with the process of embodiment 1; Different is: calcining heat changes 300 ℃ of temperature into by 500 ℃ of the temperature among the embodiment 1; Calcine 2h, obtain the Graphene of nano titanium oxide load.Shown in Fig. 4 (c), the anatase crystal that can be found out nano titanium oxide by figure is lower than degree of crystallinity among embodiment 1 and the embodiment 2 by the XRD spectra of the Graphene of the made nano titanium oxide load of present embodiment.
Embodiment 4
The process of Graphene that present embodiment prepares the load anatase-type nanometer titanium dioxide is identical with the process of embodiment 1; Different is: the titanium hydroxide colloidal solution that will in the 100ml of graphitiferous alkene ethanolic solution, add changes 5ml into by 10ml, makes the Graphene of load nano-titanium dioxide at last.
Embodiment 5
The process of Graphene that present embodiment prepares the load anatase-type nanometer titanium dioxide is identical with the process of embodiment 1; Different is: the titanium hydroxide colloidal solution that will in the 100ml of graphitiferous alkene ethanolic solution, add changes 3.3ml into by 10ml, makes the Graphene of load nano-titanium dioxide at last.
Embodiment 6
The process of Graphene that present embodiment prepares the load anatase-type nanometer titanium dioxide is identical with the process of embodiment 1; Different is: the titanium hydroxide colloidal solution that will in the 100ml of graphitiferous alkene ethanolic solution, add changes 2.5ml into by 10ml, makes the Graphene of load nano-titanium dioxide at last.
Embodiment 7
The process of Graphene that present embodiment prepares the load anatase-type nanometer titanium dioxide is identical with the process of embodiment 1; Different is: the titanium hydroxide colloidal solution that will in the 100ml of graphitiferous alkene ethanolic solution, add changes 2ml into by 10ml, makes the Graphene of load nano-titanium dioxide at last.
Claims (2)
1. the preparation method of graphene of a load anatase-type nanometer titanium dioxide is characterized in that comprising following process:
(1) preparation graphite oxide: by the H of every gram natural flake graphite with mass concentration 98%
2SO
4Ratio for 30-40ml joins H with natural flake graphite
2SO
4In, under in ice-water bath, stirring, be 5: 1 by the mass ratio of potassium permanganate and natural flake graphite, add KMnO again
4, reaction 0.5-2h, then; Mixture transferred in temperature 30-40 ℃ the water-bath, continue to stir 30～60min, be warming up to 50-70 ℃ again; Stir 0.5-2h, with deionized water 80-120mL, with the hydrogen peroxide solution 10-20mL ratio of mass concentration 30%, continue to stir down in every gram natural flake graphite; Add deionized water and hydrogen peroxide solution reaction 10-20min successively; Product is through centrifugation, and filter cake is used hydrochloric acid and deionized water wash to the sulfate radical-free ion of mass concentration 2-10% successively, in vacuum drying chamber, obtains graphite oxide in temperature 50-80 ℃ of dry 24-48h again;
(2) preparation Graphene: the graphite oxide of step (1) system is dispersed in compound concentration 0.5-1mg/ml solution in the deionized water, and the ultrasonic 2-5h that peels off obtains graphene oxide solution; In graphene oxide solution, add neopelex; The quality of neopelex and the mass ratio of graphite oxide are 1: (1-3); In graphene oxide solution, add mass concentration again and be 85% hydrazine hydrate; The volumetric usage of this hydrazine hydrate solution is by every gram graphite oxide 1-10ml, behind temperature 70-80 ℃ of water-bath backflow 24-48h, product use deionized water wash to pH be 7; The Graphene that obtains is joined in the absolute ethyl alcohol, be made into the ethanolic solution that concentration is the Graphene of 0.5-1mg/ml;
(3) preparation titanium hydroxide colloidal solution: butyl titanate splashed into to be mixed with volumetric concentration in the absolute ethyl alcohol be that the solution of 1-3% is end liquid; Under agitation in end liquid, drip mixed liquor; Described mixed liquor is that 36.5% hydrochloric acid, absolute ethyl alcohol and deionized water are by volume measured 3～4 times, 1.5～1.8 times and 1.5～1.8 times of being respectively the butyl titanate volume and formed by mass concentration, obtains titanium hydroxide colloidal solution after mixed liquor dropwises;
The ethanolic solution of the Graphene that (4) step (2) is made and the titanium hydroxide colloidal solution that step (3) makes is (10-50) by volume: 1 mixed, stir 30min-60min, and leave standstill behind the 12-24h in drying box in 60 ℃ of-80 ℃ of evaporates to dryness of temperature.After the powder that obtains ground, in argon gas atmosphere, be warming up to 300 ℃-500 ℃ by the heating rate of 10 ℃/min and calcine 2h-3h, obtain the Graphene of load anatase-type nanometer titanium dioxide.
2. the application of the Graphene of a load anatase-type nanometer titanium dioxide that makes with the described method of claim 1, the negative pole of the Graphene of this load anatase-type nanometer titanium dioxide and the mixed nickel-hydrogen secondary cell of copper powder.
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