CN102130334A - Graphene-based nano iron oxide composite material and preparation method thereof - Google Patents
Graphene-based nano iron oxide composite material and preparation method thereof Download PDFInfo
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- CN102130334A CN102130334A CN2011100249909A CN201110024990A CN102130334A CN 102130334 A CN102130334 A CN 102130334A CN 2011100249909 A CN2011100249909 A CN 2011100249909A CN 201110024990 A CN201110024990 A CN 201110024990A CN 102130334 A CN102130334 A CN 102130334A
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Abstract
The invention discloses a graphene-based nano iron oxide composite material and a preparation method thereof. By the method, iron oxide nano granules with uniform diameter and controllable shape and components can be loaded on graphene. The method comprises the following steps of: uniformly dispersing graphite oxide into deionized water by adopting an ultrasonic method to obtain graphene oxide solution; adding an iron salt precursor into the obtained solution and mixing the precursor and the solution uniformly, adjusting the pH of the solution, and hydrolyzing the iron salt; putting the mixed solution into a reaction kettle and performing hydrothermal reaction; and finally, cleaning and freeze-drying the obtained product to obtain the graphene-based nano iron oxide composite material. The raw materials are common and easily obtained, the cost is low, and the preparation process is simple, safe and environmentally-friendly; the prepared graphene-based nano iron oxide composite material has good structural stability and monodispersity; when the composite material is used as a lithium iron battery electrode material, the charge/discharge capacity can reach over 1,000mAh/g; and the composite material has good multiplying power performance and cycle life.
Description
Affiliated technical field
The present invention relates to a kind of graphene-based nano-iron oxide composite material, particularly a kind of graphene-based nano-iron oxide composite material and preparation method thereof belongs to the new function technical field of composite materials.
Background technology
Graphene is a kind of novel two-dimentional carbon nanomaterial, by the tightly packed one-tenth bi-dimensional cellular of individual layer atom shape structure.Studies show that Graphene has big specific area, superpower conductivity, better chemical stability and broad a series of excellent properties such as electrochemical stability window.Recent study person finds, carry out nano combinedization with Graphene, can significantly improve the performances such as hardness, conductivity and electrochemistry capacitance of material.People such as Wang H have reported that on JACS 2010 13978-13980 employing two-step method liquid phase reactor prepares Mn
3O
4-graphene composite material during used as lithium ion battery electrode material, has the lithium storage content up to 900mA/g, and shows good high rate performance and cycle performance.People such as Yang S have reported Graphene encapsulation oxide nano material on AngewChem Int Ed 20108408-8411, have the lithium storage content near theoretical capacity, also show good high rate performance and cycle performance simultaneously.
Ferriferous oxide (Fe
2O
3, Fe
3O
4And FeO) be that a class has the functional material than multipurpose, wherein di-iron trioxide and tri-iron tetroxide have the lithium ion battery electrode material of new generation that high theoretical lithium storage content, low cost, nontoxic pollution-free etc. are regarded as having potentiality because of it.When yet this class material was used as lithium ion battery electrode material, enclosed pasture efficient was lower first usually, and the Reversible Cycle capacity attenuation is very fast, and has serious voltage delay phenomenon.Therefore the composite material for preparing ferriferous oxide is most important to improve its conductivity and to suppress its change in volume.Modification to ferriferous oxide mainly is by chemical method that itself and material with carbon element is compound at present, adopt carbon sources such as carbon nano-tube, graphite, acetylene black that ferriferous oxide is carried out coating modification, but the general capacity of the silicon/iron oxide composite material of preparing is lower.Rarely has bibliographical information and be prepared into nano composite material correlative study work about Graphene and ferriferous oxide so far.Mainly there is following shortcoming in the method for the graphene-based ferriferous oxide nano composite material of current preparation: preparation process is comparatively loaded down with trivial details, prepare effective dispersion that Graphene can not guarantee Graphene by reducing agent, even the reunion of Graphene and heavy problem such as accumulation can occur; Not only cost of material is higher as dispersion solvent and adopt organic solvent, and has certain toxicity and potential safety hazard, simultaneously because the complexity of reaction is difficult to guarantee product quality stability.Therefore the effective ways of seeking out low cost, the graphene-based ferriferous oxide nano composite material of eco-friendly preparation are still the research focus.Adopt the research of the graphene-based ferriferous oxide nano composite material of Hydrothermal Preparation then not appear in the newspapers at present.
Summary of the invention
The purpose of this invention is to provide a kind of graphene-based ferriferous oxide nano composite material and preparation method thereof, this method can make graphene-supported go up particle diameter evenly, pattern, the controlled iron oxide nanoparticles of component; When prepared graphene base nano-iron oxide composite material was used as lithium ion battery electrode material, charge/discharge capacity can reach more than the 1000mAh/g, and has high rate performance and cycle life preferably; Require technology simple, with low cost simultaneously, environmental friendliness is fit to suitability for industrialized production.
Realize that technical scheme of the present invention is: with graphite oxide, molysite and ferrous salt presoma is raw material, mixes by mechanical agitation earlier, utilizes one step of hydro-thermal reaction to make graphene-based silicon/iron oxide composite material then.Its concrete steps are:
(1) a certain amount of graphite oxide is dissolved in the deionized water, ultrasonic dispersion obtained the graphene oxide dispersion liquid in 30～120 minutes;
(2) the graphene oxide dispersion liquid is placed protective atmosphere, add a certain proportion of molysite precursor mixed solution, stirred 20～60 minutes, add a certain amount of aqueous slkali, making pH of mixed is 2.5～11, continues to stir 30～90 minutes;
(3) above-mentioned mixed liquor is transferred to hydrothermal reaction kettle, 100～250 ℃ were reacted 4～40 hours down;
(4) will react resultant product and use absolute ethyl alcohol and washed with de-ionized water respectively, obtain graphene-based ferriferous oxide nano composite material after the vacuum freeze drying.
Said protective atmosphere in the step (2) can be nitrogen or argon gas; Said (Asia) iron salt solutions in the step (2) can be sulfuric acid (Asia) iron, chlorination (Asia) iron, the mixed solution of one or several in the hydrated salt of nitric acid (Asia) iron and oxalic acid (Asia) iron; Said aqueous slkali in the step (2) can be one or several the mixed solution in NaOH, ammoniacal liquor, sodium carbonate or the urea; The said cleaning method of step (4) comprises two kinds of methods of filtration method and centrifugal process.
Characteristics of the present invention are by mechanical agitation, earlier two kinds of precursor material are evenly mixed, and utilize one step of hydro-thermal reaction to make graphene-based ferriferous oxide nano composite material then.Its advantage is that raw material is common and is easy to get that with low cost, preparation process is simple and safe, and each step does not produce poisonous and harmful substance in the preparation process; In the products therefrom, iron oxide particle can evenly divide and is spread on the Graphene surface, and stronger adhesion is arranged between the two, has both avoided the reunion of self particle, has also effectively prevented heavily piling up of Graphene lamella.Structural advantage makes it have excellent comprehensive performances, has multiple field potential application is all arranged.
Description of drawings
Fig. 1 XRD figure spectrum of the present invention.
Fig. 2 SEM Electronic Speculum of the present invention picture; Wherein a is the SEM figure of graphene-based ferriferous oxide nano composite material among the embodiment 1; B is the SEM figure of graphene-based ferriferous oxide nano composite material among the embodiment 2.
Fig. 3 the present invention is as the charging and discharging curve of lithium ion cell electrode.
Fig. 4 the present invention is as the cycle performance curve of lithium ion cell electrode.
Fig. 5 the present invention is as the high rate performance curve of lithium ion cell electrode.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is described further.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition and do not deviate from spirit and scope of the invention the present invention is carried out various changes and modifications all is conspicuous for a person skilled in the art that these equivalent form of values fall within the application equally and say attached claims institute restricted portion.
Embodiment one:
The 1g graphite oxide is added in the 500ml deionized water, obtained the graphene oxide dispersion liquid in ultrasonic 1 hour, simultaneously with 3.5g Iron(III) chloride hexahydrate solution deionized water.Above-mentioned two kinds of solution are mixed in the round-bottomed flask of packing into, stirred 30 minutes, add ammoniacal liquor gradually, the pH to 4 of regulator solution.At the bottom of this gel transferred to hydrothermal reaction kettle, 150 ℃ of reactions 12 hours down.Hydrothermal product is used absolute ethyl alcohol and deionized water eccentric cleaning respectively for several times, after the vacuum freeze drying, obtain graphene-based ferriferous oxide nano composite material.
Fig. 1 is the XRD figure after the annealed again heat treatment of composite material that obtains of embodiment 1.By mainly containing di-iron trioxide in visible this composite material of the diffraction maximum of Fig. 1.
Fig. 2 a is the SEM figure after the prepared annealed again heat treatment of composite material of embodiment 1.As seen from the figure, iron oxide particle is dispersed in the Graphene surface in the graphene-based ferriferous oxide nano composite material that obtains among the embodiment 1, and particle diameter is at 20～30nm.
To the composite material that the makes heat treatment of annealing.Graphene-based ferriferous oxide nano composite material electrode is formed by the mass percent of the Kynoar adhesive of 80% graphene-based ferriferous oxide nano composite material and 20%; Electrolyte is 1mol/L LiPF
6-EC (ethylene carbonate)+DEC (diethyl carbonate)+DMC (dimethyl carbonate) (mass ratio is 1: 1: 1) is assembled into button cell.Discharge and recharge experiment and finish in 2032 type button cells, the lithium metal conduct is to electrode; Barrier film is Celgard 2300.
Fig. 3 and Fig. 4 are respectively charging and discharging curve and the cyclic curve that with the current density of 50mA/g battery is carried out charge-discharge test under the room temperature in 3～0.001V scope.As seen from the figure, the graphene-based ferriferous oxide nano composite material that the present invention makes has the specific capacity up to 1000mAh/g, and has good cyclical stability during as lithium ion battery electrode material.Fig. 5 is for carrying out the cyclic curve of charge-discharge test to battery with different current densities in 3～0.1V scope under the room temperature.Can see that the graphene-based ferriferous oxide nano composite material that the present invention makes has good high rate performance.
Embodiment two:
The 1g graphite oxide is added in the 500ml deionized water, obtained the graphene oxide dispersion liquid in ultrasonic 2 hours, simultaneously with 10g Iron(III) chloride hexahydrate solution deionized water.Above-mentioned two kinds of solution are mixed in the round-bottomed flask of packing into, stirred 30 minutes, add sodium hydroxide solution gradually, the pH to 10 of regulator solution fully precipitates iron ion.At the bottom of this gel transferred to hydrothermal reaction kettle, 180 ℃ of reactions 20 hours down.Hydrothermal product is filtered cleaning for several times with absolute ethyl alcohol and deionized water, obtain graphene-based ferriferous oxide nano composite material after the vacuum freeze drying.
Fig. 2 b is the SEM figure after the prepared annealed again heat treatment of composite material of embodiment 2.As seen from the figure, iron oxide particle is dispersed in the Graphene surface in the graphene-based ferriferous oxide nano composite material that obtains among the embodiment 2.
Claims (9)
1. graphene-based ferriferous oxide nano composite material is characterized in that by the following steps preparation and gets:
(1) graphite oxide is added to ultrasonic dispersion in the water, forms with the homodisperse graphene oxide solution of monolithic layer;
(2) under the protective atmosphere, in gained graphene oxide solution, add iron salt solutions, and add aqueous slkali, mix;
(3) above-mentioned mixed liquor is transferred to reactor and carries out hydro-thermal reaction;
(4) reaction finishes, and with resultant product cleaning, obtains graphene-based ferriferous oxide nano composite material after the drying.
2. graphene-based ferriferous oxide nano composite material according to claim 1 is characterized in that: the ratio of water and the consumption of graphite oxide 1: 1～2000: 1, the mass ratio of graphite oxide and molysite (by Iron(III) chloride hexahydrate) 20: 1～1: 100.
3. graphene-based ferriferous oxide nano composite material according to claim 1 is characterized in that: the pH that adds the alkali lye regulator solution is all between 2.5～11.
4. graphene-based ferriferous oxide nano composite material according to claim 1 is characterized in that: the temperature range of hydro-thermal reaction is between 100～250 ℃, and the reaction time is between 4～40 hours.
5. graphene-based ferriferous oxide nano composite material according to claim 1 is characterized in that: the process of described cleaning is to clean repeatedly with in centrifugal process or the filtration method one or both, cleans solvent for use and be in water or the ethanol one or both.
6. graphene-based ferriferous oxide nano composite material according to claim 1 is characterized in that: described dry run is to adopt vacuum freeze-drying method, and dry temperature is between-80～10 ℃, and pressure is between 0～101kPa, and the time is at 6～72h.
7. graphene-based ferriferous oxide nano composite material according to claim 1 is characterized in that: described molysite presoma is the water of chlorination (Asia) iron, sulfuric acid (Asia) iron, nitric acid (Asia) iron or oxalic acid (Asia) iron and in the salt one or more.
8. graphene-based ferriferous oxide nano composite material according to claim 1 is characterized in that: described ferriferous oxide is ferrous oxide, di-iron trioxide, tri-iron tetroxide.
9. graphene-based ferriferous oxide nanometer combined electrode material, it is characterized in that: graphene-based ferriferous oxide nano composite material is heat-treated, heat treated temperature is between 200～800 ℃, and the time, heating rate was between 0.1～20 ℃/min between 0.5～24h.
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| CN102603014A (en) * | 2011-10-08 | 2012-07-25 | 北京中科微纳物联网技术股份有限公司 | Environment-friendly and efficient method for preparing iron sesquioxide/graphene composite material |
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