CN102130334B - 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 PDF

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CN102130334B
CN102130334B CN2011100249909A CN201110024990A CN102130334B CN 102130334 B CN102130334 B CN 102130334B CN 2011100249909 A CN2011100249909 A CN 2011100249909A CN 201110024990 A CN201110024990 A CN 201110024990A CN 102130334 B CN102130334 B CN 102130334B
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graphene
composite
solution
iron
iron oxide
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CN2011100249909A
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CN102130334A (en
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田雷雷
庄全超
吴超
李佳
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中国矿业大学
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    • 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 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

Graphene-based nano iron oxide composite material and preparation method thereof
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, belong to the new function technical field of composite materials.
Background technology
Graphene is a kind of New Two Dimensional carbon nanomaterial, by the tightly packed one-tenth bi-dimensional cellular of individual layer atom shape structure.Research shows, Graphene has large specific area, superpower conductivity, chemical stability and broad a series of excellent properties such as electrochemical stability window preferably.Recent study person finds, with Graphene, carry out nano combinedization, can significantly improve the performances such as hardness, conductivity and electrochemistry capacitance of material.The 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, have the lithium storage content up to 900mA/g, and show good high rate performance and cycle performance.The people such as Yang S have reported Graphene encapsulation oxide nano material on AngewChem Int Ed 20108408-8411, have the lithium storage content that approaches 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 more multiduty functional material, wherein di-iron trioxide and tri-iron tetroxide have because of it 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.When yet this class material is used as lithium ion battery electrode material, enclosed pasture efficiency is 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.Be mainly by chemical method, that itself and material with carbon element is compound to the modification of ferriferous oxide at present, adopt the carbon sources such as carbon nano-tube, graphite, acetylene black to be coated modification to ferriferous oxide, but the general capacity of the silicon/iron oxide composite material of preparing be 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 by reducing agent effective dispersion that Graphene can not guarantee Graphene, even there will be the reunion of Graphene and the heavy problem such as accumulation; And adopt organic solvent, as dispersion solvent, not only cost of material is higher, and has certain toxicity and potential safety hazard, simultaneously due to the complexity of reaction, is difficult to guarantee the quality stability of product.Therefore the effective ways of finding out low cost, the graphene-based ferriferous oxide nano composite material of eco-friendly preparation are still study hotspot.The research that adopts at present hydro thermal method to prepare graphene-based ferriferous oxide nano composite material has no report.
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, the method can make graphene-supported upper particle diameter evenly, pattern, the controlled iron oxide nanoparticles of component; When prepared graphene-based nano iron oxide composite material is used as lithium ion battery electrode material, more than charge/discharge capacity can reach 1000mAh/g, and there is high rate performance and cycle life preferably; Require technique simple, with low cost, environmental friendliness, be applicable to suitability for industrialized production simultaneously.
Realize that technical scheme of the present invention is: take graphite oxide, molysite and ferrous salt presoma is raw material, first by mechanical agitation, mixes, and then utilizes hydro-thermal reaction one step to make graphene-based silicon/iron oxide composite material.Its concrete steps are:
(1) a certain amount of graphite oxide is dissolved in deionized water, ultrasonic dispersion obtains the graphene oxide dispersion liquid in 30~120 minutes;
(2) the graphene oxide dispersion liquid is placed in to protective atmosphere, adds a certain proportion of molysite precursor mixed solution, stir 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, reacts 4~40 hours under 100~250 ℃;
(4) will react resulting product and use respectively absolute ethyl alcohol and washed with de-ionized water, obtain graphene-based ferriferous oxide nano composite material after vacuum freeze drying.
Said protective atmosphere in step (2) can be nitrogen or argon gas; Said (Asia) iron salt solutions in 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 step (2) can be one or several the mixed solution in NaOH, ammoniacal liquor, sodium carbonate or urea; The said cleaning method of step (4), comprise two kinds of methods of filtration method and centrifugal process.
Characteristics of the present invention are by mechanical agitation, first two kinds of precursor material are evenly mixed, and then utilize hydro-thermal reaction one step to make graphene-based ferriferous oxide nano composite material.Its advantage is that raw material is common and is easy to get, and with low cost, preparation process is simple and safe, and in preparation process, each step does not produce poisonous and harmful substance; In 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 that the weight of graphene sheet layer is stacking.Structural advantage makes it have good combination property, has multiple fields potential application is arranged.
The accompanying drawing explanation
Fig. 1 XRD collection of illustrative plates 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 in embodiment 1; B is the SEM figure of graphene-based ferriferous oxide nano composite material in 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 are not used in and limit the scope of the invention for the present invention is described.Should be understood that in addition and do not deviate from spirit and scope of the invention the present invention is carried out to various changes and modifications is all apparent for a person skilled in the art, these equivalent form of values fall within equally the application and say attached claims limited range.
Embodiment mono-:
The 1g graphite oxide is added in the 500ml deionized water, within ultrasonic 1 hour, obtain the graphene oxide dispersion liquid, simultaneously by 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, stir 30 minutes, add gradually ammoniacal liquor, the pH to 4 of regulator solution.At the bottom of this gel is transferred to hydrothermal reaction kettle, reaction is 12 hours under 150 ℃.Hydrothermal product is used respectively to absolute ethyl alcohol and deionized water eccentric cleaning for several times, after vacuum freeze drying, obtain graphene-based ferriferous oxide nano composite material.
Fig. 1 is the composite material that obtains of the embodiment 1 XRD figure after annealed heat treatment again.Mainly contain di-iron trioxide in visible this composite material of the diffraction maximum of Fig. 1.
Fig. 2 a is the prepared composite material of embodiment 1 figure of the SEM after annealed heat treatment again.As seen from the figure, in the graphene-based ferriferous oxide nano composite material obtained in embodiment 1, iron oxide particle is dispersed in the Graphene surface, and particle diameter is at 20~30nm.
To the composite material the made heat treatment of being annealed.Graphene-based ferriferous oxide nano composite material electrode forms 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), be assembled into button cell.Discharge and recharge experiment and complete in 2032 type button cells, lithium metal is as to electrode; Barrier film is Celgard 2300.
Fig. 3 and Fig. 4 are respectively under room temperature the current density with 50mA/g in 3~0.001V scope and battery are carried out to charging and discharging curve and the cyclic curve of charge-discharge test.As seen from the figure, the graphene-based ferriferous oxide nano composite material that the present invention makes during as lithium ion battery electrode material, has the specific capacity up to 1000mAh/g, and has good cyclical stability.Fig. 5 carries out the cyclic curve of charge-discharge test in 3~0.1V scope to battery with different current densities under room temperature.Can see, the graphene-based ferriferous oxide nano composite material that the present invention makes has good high rate performance.
Embodiment bis-:
The 1g graphite oxide is added in the 500ml deionized water, within ultrasonic 2 hours, obtain the graphene oxide dispersion liquid, simultaneously by 10g Iron(III) chloride hexahydrate solution deionized water.Above-mentioned two kinds of solution are mixed in the round-bottomed flask of packing into, stir 30 minutes, add gradually sodium hydroxide solution, the pH to 10 of regulator solution, fully precipitate iron ion.At the bottom of this gel is transferred to hydrothermal reaction kettle, reaction is 20 hours under 180 ℃.Hydrothermal product is filtered and cleans for several times with absolute ethyl alcohol and deionized water, obtain graphene-based ferriferous oxide nano composite material after vacuum freeze drying.
Fig. 2 b is the prepared composite material of embodiment 2 figure of the SEM after annealed heat treatment again.As seen from the figure, in the graphene-based ferriferous oxide nano composite material obtained in embodiment 2, iron oxide particle is dispersed in the Graphene surface.

Claims (2)

1. a graphene-based ferriferous oxide nano composite material, it is characterized in that, by the following steps preparation, obtained: the 1g graphite oxide is added in the 500ml deionized water, within ultrasonic 1 hour, obtain the graphene oxide dispersion liquid, the 3.5g Iron(III) chloride hexahydrate is dissolved in to deionized water simultaneously; Above-mentioned two kinds of solution are mixed in the round-bottomed flask of packing into, stir 30 minutes, add gradually ammoniacal liquor, the pH to 4 of regulator solution; At the bottom of this gel is transferred to hydrothermal reaction kettle, reaction is 12 hours under 150 ℃; Hydrothermal product is used respectively to absolute ethyl alcohol and deionized water eccentric cleaning for several times, after vacuum freeze drying, obtain graphene-based ferriferous oxide nano composite material.
2. graphene-based ferriferous oxide nano composite material according to claim 1, it is characterized in that: described graphene-based ferriferous oxide nano composite material is heat-treated, heat treated temperature is between 200~800 ℃, time, heating rate was between 0.1~20 ℃/min between 0.5~24h.
CN2011100249909A 2011-01-15 2011-01-15 Graphene-based nano iron oxide composite material and preparation method thereof CN102130334B (en)

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