CN103531789A - Iron oxide-carbon nanotube ternary composite material and preparation method thereof - Google Patents

Iron oxide-carbon nanotube ternary composite material and preparation method thereof Download PDF

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Publication number
CN103531789A
CN103531789A CN201210577429.8A CN201210577429A CN103531789A CN 103531789 A CN103531789 A CN 103531789A CN 201210577429 A CN201210577429 A CN 201210577429A CN 103531789 A CN103531789 A CN 103531789A
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composite material
ternary composite
nanometer pipe
carbon nanometer
carbon nanotube
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CN201210577429.8A
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庄全超
吴超
田雷雷
章新喜
崔永丽
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China University of Mining and Technology CUMT
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China University of Mining and Technology CUMT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses an iron oxide-carbon nanotube ternary composite material and a preparation method thereof. According to the method, Fe3O4 and Fe2O3 particles with controllable shapes and components are evenly distributed in a three-dimensional network of a carbon nanotube. The method comprises the following steps: firstly, evenly dispersing the functionalized carbon nanotubes and iron salt in deionized water; then adding an alkaline solution into the deionized water and regulating the pH (Potential Of Hydrogen) of the mixed solution; performing hydrothermal reaction on the mixed solution in a reaction kettle; cleaning and drying an obtained precursor; and finally, calcining an obtained product so as to obtain a Fe3O4-Fe2O3-carbon nanotube ternary composite material in a shape of black powder. The method has the advantages of simplicity, safety, environmental protection and no pollution in preparation process. The prepared Fe3O4-Fe2O3-carbon nanotube ternary composite material is good in structure stability and monodispersity. When the Fe3O4-Fe2O3-carbon nanotube ternary composite material is taken as a negative electrode material of a lithium ion battery, the discharge capacity of the composite material exceeds 1000mAh/g; the composite material is long in cycle life and good in rate performance.

Description

A kind of ferriferous oxide-carbon nanometer pipe ternary composite material and preparation method thereof
Technical field
The present invention relates to a kind of preparation method of ferriferous oxide-carbon nanometer pipe ternary composite material, particularly a kind of Fe 3o 4-Fe 2o 3the preparation method of-carbon nanometer pipe ternary composite material, belongs to nano material and chemical power source technology art field.
Background technology
As high-energy secondary battery product of new generation, the outstanding advantages such as lithium ion battery has that operating voltage is high, high-energy-density, long circulation life and environmental friendliness, be widely used in the portable sets such as mobile phone, notebook computer, Mp3 player, digital camera and video camera, and progressively in electric tool, electric automobile, hybrid vehicle and energy storage field, obtained application.Be accompanied by the demand that it grows with each passing day, lithium ion battery is just becoming emphasis and the focus of scientific and technical research and exploitation.
At present, commercial lithium-ion batteries electrode material used is embedding off-type electrode material, and due to structural restriction, the theoretical memory capacity of lithium ion is low, has become the bottleneck of the further raising of capacity of lithium ion battery.The exploitation that is lithium ion battery electrode material of new generation for the research of the transition metal oxide based on reversible conversion reaction mechanism provides the new visual field, because this class material has conventionally more than the high theoretical lithium storage content of graphite material.Wherein, Fe 2o 3there is advantages such as surpassing the theoretical lithium storage content of 1000mAh/g and low cost, nontoxic pollution-free, be more subject to broad research.From the angle of practical application, one-component Fe 2o 3although higher as electrode material theoretical capacity, the problem of 2 aspects below existing: (1) Fe 2o 3the conductivity of particle is poor, there is serious voltage delay phenomenon, be between its charging voltage and discharge voltage, to have larger difference, cause lower energy efficiency to have serious voltage delay phenomenon, be between its charging voltage and discharge voltage, to have larger difference, cause lower energy efficiency; (2) Fe 2o 3when nano particle reacts with lithium ion, can there is larger volumetric expansion, produce larger stress, cause electrode material activity particle to lose good contact broken, cause Reversible Cycle capacity attenuation very fast.At present to Fe 2o 3the modification of electrode material is mainly by chemical method, itself and material with carbon element is compound, adopts the Fes of carbon source to one-component such as carbon nano-tube, graphite, acetylene black 2o 3nano particle is coated modification, but the general capacity of the silicon/iron oxide composite material of preparing is lower.Fe 3o 4there is good conductivity, but its theoretical capacity is relatively low.If by Fe 2o 3and Fe 3o 4simultaneously compound with carbon source, prepare the Fe with excellent comprehensive electrochemical 3o 4-Fe 2o 3-carbon nanometer pipe ternary composite material, greatly degree improves conductivity and the structural stability of electrode material inside, can not lose larger theoretical capacity again simultaneously, be work highly significant, and this composite material has no bibliographical information at present.
Summary of the invention
The object of this invention is to provide a kind of Fe 3o 4-Fe 2o 3-carbon nanometer pipe ternary composite material and preparation method thereof.The method can make size, pattern, the controlled Fe of component 3o 4-Fe 2o 3nano particle is evenly distributed in the carbon nano-tube with tridimensional network; Prepared Fe 3o 4-Fe 2o 3when-carbon nanometer pipe ternary composite material is used as lithium ion battery electrode material, more than discharge capacity can reach 1000 mAh/g, and there is good cycle performance and high rate performance; Have preparation technology simple, advantages of environment protection, can carry out large-scale production simultaneously.
Realizing technical scheme of the present invention is: take molysite and carbon nano-tube as raw material, first by mechanical agitation, mix, then adopt hydro-thermal reaction legal system to obtain persursor material, finally roasting obtains Fe under certain condition 3o 4-Fe 2o 3-carbon nanometer pipe ternary composite material.Its concrete steps are:
(1) molysite of a ratio and carbon nano-tube are dissolved in deionized water, ultrasonic dispersion obtains uniform mixed solution for 10 ~ 120 minutes;
(2) add a certain amount of aqueous slkali, making pH of mixed is 3 ~ 11, continues to stir;
(3) above-mentioned mixed liquor is transferred to hydrothermal reaction kettle, reacts 1 ~ 48 hour at 90 ~ 250 ℃;
(4) will react resulting product and with deionized water and absolute ethyl alcohol, clean respectively, after vacuum freeze drying, obtain persursor material;
(5) by persursor material 300 ~ 600 ℃ of roastings 0.5 ~ 24 hour under air atmosphere, be cooled to room temperature, obtain Fe 3o 4-Fe 2o 3-carbon nanometer pipe ternary composite material.
Said molysite in step (1), can be ferric sulfate, iron chloride, the composition of one or several in the hydrated salt of ferric nitrate and ferric oxalate; Said aqueous slkali in step (2) can be one or several the combination solution in NaOH, ammoniacal liquor, sodium carbonate or urea; The said cleaning method of step (4), comprises two kinds of methods of filtration method and centrifugal process.
Feature of the present invention is by mechanical agitation, first two kinds of raw materials is evenly mixed, and then utilizes hydro-thermal reaction one step to make persursor material, and finally under air atmosphere, roasting obtains Fe 3o 4-Fe 2o 3-carbon nanometer pipe ternary composite material.Its advantage is that preparation technology is simple and safe, and in preparation process, each step does not produce poisonous and harmful substance; In products therefrom, Fe 3o 4-Fe 2o 3nano particle can be evenly distributed in the carbon nano-tube with tridimensional network, and resulting materials has very high reversible lithium storage capacity, has good cycle performance simultaneously.Fe 3o 4-Fe 2o 3-carbon nanometer pipe ternary composite material has the advantages such as Stability Analysis of Structures, good conductivity, thereby possesses good combination property, at multiple fields, has potential application.
Accompanying drawing explanation
Fig. 1 is by the Fe of example 1 synthesized 3o 4-Fe 2o 3the X-ray diffraction of-carbon nanometer pipe ternary composite material (XRD) collection of illustrative plates.
Fig. 2 is by the Fe of example 1 synthesized 3o 4-Fe 2o 3-carbon nanometer pipe ternary composite material is observed the pattern obtaining under ESEM.
Fig. 3 is by the Fe of example 1 synthesized 3o 4-Fe 2o 3the charging and discharging curve of-carbon nanometer pipe ternary composite material under 100mA/g current density.
Fig. 4 is by the Fe of example 1 synthesized 3o 4-Fe 2o 3the stable circulation linearity curve of-carbon nanometer pipe ternary composite material under 100mA/g current density.
Fig. 5 is by the Fe of example 1 synthesized 3o 4-Fe 2o 3the stable circulation linearity curve of-carbon nanometer pipe ternary composite material under different current densities.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is described further.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that 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 carbon nano-tube that 6.75g ferric chloride hexahydrate and 0.67g had been activated adds in 400ml deionized water, and supersonic oscillations obtain uniform mixed solution for 0.5 hour.Upper mixed solution is packed in round-bottomed flask, stir 30 minutes, add gradually NaOH, the pH to 6 of regulator solution.At the bottom of this mixed solution is transferred to hydrothermal reaction kettle, react 12 hours at 160 ℃.Hydrothermal product is used respectively to deionized water and absolute ethyl alcohol eccentric cleaning for several times, after vacuum freeze drying, obtain persursor material.By persursor material roasting 2 hours under 400 ℃ of air atmospheres, be cooled to room temperature, obtain Fe 3o 4-Fe 2o 3-carbon nanometer pipe ternary composite material.
Fig. 1 is the Fe that embodiment 1 obtains 3o 4-Fe 2o 3the XRD figure of-carbon nanometer pipe ternary composite material.By visible this composite material of the diffraction maximum of Fig. 1 by Fe 3o 4, Fe 2o 3form with three kinds of materials of carbon nano-tube.
Fig. 2 is the prepared Fe of embodiment 1 3o 4-Fe 2o 3the SEM figure of-carbon nanometer pipe ternary composite material.As seen from the figure, the Fe obtaining in embodiment 1 3o 4-Fe 2o 3fe in-carbon nanometer pipe ternary composite material 3o 4-Fe 2o 3nano particle is dispersed in the carbon nano-tube with tridimensional network.
Fe 3o 4-Fe 2o 3/ carbon nano tube compound material electrode is pressed 80% Fe 3o 4-Fe 2o 3the mass percent of-carbon nanometer pipe ternary composite material and 20% Kynoar adhesive forms; Electrolyte is 1 mol/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 complete in 2032 type button cells, lithium metal is as to electrode; Barrier film is Celgard 2300.
Fig. 3 and Fig. 4 are respectively the charging and discharging curve and the steady performance curve of circulation that with the current density of 100mA/g, battery is carried out charge-discharge test under room temperature within the scope of 3 ~ 0.005V.As seen from the figure, the Fe that the present invention makes 3o 4-Fe 2o 3-carbon nanometer pipe ternary composite material during as lithium ion battery electrode material, has up to specific capacity more than 1000mAh/g, and stable cycle performance.Fig. 5 carries out the cycle performance curve of charge-discharge test within the scope of 3 ~ 0.005V to battery with different current densities under room temperature.Can find out the Fe that the present invention makes 3o 4-Fe 2o 3-carbon nanometer pipe ternary composite material has good high rate performance.
Embodiment bis-:
The carbon nano-tube that 8.1g ferric chloride hexahydrate and 0.8g had been activated adds in 500ml deionized water, and supersonic oscillations obtain uniform mixed solution for 1 hour.Upper mixed solution is packed in round-bottomed flask, stir 30 minutes, add gradually NaOH, the pH to 9 of regulator solution.At the bottom of this mixed solution is transferred to hydrothermal reaction kettle, react 12 hours at 180 ℃.Hydrothermal product is used respectively to deionized water and absolute ethyl alcohol eccentric cleaning for several times, after vacuum freeze drying, obtain persursor material.By persursor material roasting 2 hours under 600 ℃ of air atmospheres, be cooled to room temperature, obtain Fe 3o 4-Fe 2o 3-carbon nanometer pipe ternary composite material.

Claims (6)

1. ferriferous oxide-carbon nanometer pipe ternary composite material, is characterized in that being prepared and being obtained by following steps:
(1) molysite and the carbon nano-tube that activated are joined to deionized water for ultrasonic and disperse, form uniform mixed solution;
(2) in the mixed solution of gained, add aqueous slkali, regulator solution pH value;
(3) above-mentioned mixed liquor is transferred to reactor and carries out hydro-thermal reaction;
(4) react complete, resulting persursor material is cleaned, dry, roasting under air atmosphere, finally obtains Fe 3o 4-Fe 2o 3-carbon nanometer pipe ternary composite material.
2. a kind of ferriferous oxide-carbon nanometer pipe ternary composite material according to claim 1, is characterized in that: the mass ratio 50:1 ~ 1:50 of molysite (by Iron(III) chloride hexahydrate) and carbon nano-tube.
3. a kind of ferriferous oxide-carbon nanometer pipe ternary composite material according to claim 1, is characterized in that: add the pH of alkali lye regulator solution between 3 ~ 11.
4. a kind of ferriferous oxide-carbon nanometer pipe ternary composite material according to claim 1, is characterized in that: the temperature range of hydro-thermal reaction is between 90 ~ 250 ℃, and the reaction time is between 1 ~ 48 hour.
5. a kind of ferriferous oxide-carbon nanometer pipe ternary composite material according to claim 1, it is characterized in that: described dry run is to adopt vacuum freeze-drying method, dry temperature is between-60 ~ 10 ℃, and pressure is between 0 ~ 101kPa, and the time was at 6 ~ 72 hours.
6. a kind of ferriferous oxide-carbon nanometer pipe ternary composite material according to claim 1, it is characterized in that: the persursor material obtaining after hydro-thermal reaction is carried out to roasting, the temperature of roasting is between 300 ~ 600 ℃, time, heating rate was between 0.1 ~ 10 ℃/min between 0.5 ~ 24 hour.
CN201210577429.8A 2012-12-27 2012-12-27 Iron oxide-carbon nanotube ternary composite material and preparation method thereof Pending CN103531789A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105140508A (en) * 2015-07-28 2015-12-09 南京理工大学 Method for preparing anode material Fe3O4/multi-wall carbon nanotube (MCNT) of lithium ion battery by hydrothermal method
CN107026266A (en) * 2017-06-05 2017-08-08 深圳职业技术学院 A kind of lithium ion battery CNTs/Fe2O3The preparation method of/C composite negative pole materials
CN108666538A (en) * 2017-04-01 2018-10-16 清华大学 Lithium ion battery
CN110712400A (en) * 2019-09-06 2020-01-21 天津大学 Method for preparing layered carbon fiber electromagnetic shielding composite material by using three-dimensional carbon/ferroferric oxide Koch layered layer
CN111847524A (en) * 2020-07-23 2020-10-30 国电科学技术研究院有限公司 Fe3O4/Fe2O3Magnetic heteroplasmon nanotube and preparation method thereof
CN112551652A (en) * 2020-12-11 2021-03-26 中国环境科学研究院 Surface water fluorine removal process based on carbon nano tube three-dimensional electrode

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CN102646817A (en) * 2011-02-16 2012-08-22 中国科学院金属研究所 Graphene/metal oxide composite cathode material for lithium ion battery and preparation

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105140508A (en) * 2015-07-28 2015-12-09 南京理工大学 Method for preparing anode material Fe3O4/multi-wall carbon nanotube (MCNT) of lithium ion battery by hydrothermal method
CN108666538A (en) * 2017-04-01 2018-10-16 清华大学 Lithium ion battery
CN107026266A (en) * 2017-06-05 2017-08-08 深圳职业技术学院 A kind of lithium ion battery CNTs/Fe2O3The preparation method of/C composite negative pole materials
CN107026266B (en) * 2017-06-05 2019-04-09 深圳职业技术学院 A kind of lithium ion battery CNTs/Fe2O3The preparation method of/C composite negative pole material
CN110712400A (en) * 2019-09-06 2020-01-21 天津大学 Method for preparing layered carbon fiber electromagnetic shielding composite material by using three-dimensional carbon/ferroferric oxide Koch layered layer
CN110712400B (en) * 2019-09-06 2021-10-08 天津大学 Method for preparing layered carbon fiber electromagnetic shielding composite material by using three-dimensional carbon/ferroferric oxide Koch layered layer
CN111847524A (en) * 2020-07-23 2020-10-30 国电科学技术研究院有限公司 Fe3O4/Fe2O3Magnetic heteroplasmon nanotube and preparation method thereof
CN111847524B (en) * 2020-07-23 2023-07-04 国家能源集团科学技术研究院有限公司 Fe (Fe) 3 O 4 /Fe 2 O 3 Magnetic heterogeneous nanotube and preparation method thereof
CN112551652A (en) * 2020-12-11 2021-03-26 中国环境科学研究院 Surface water fluorine removal process based on carbon nano tube three-dimensional electrode
CN112551652B (en) * 2020-12-11 2022-01-14 中国环境科学研究院 Surface water fluorine removal process based on carbon nano tube three-dimensional electrode

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Application publication date: 20140122