CN103579581A - Monocrystalline porous iron oxide powder material and preparation method thereof - Google Patents

Monocrystalline porous iron oxide powder material and preparation method thereof Download PDF

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CN103579581A
CN103579581A CN201310536673.4A CN201310536673A CN103579581A CN 103579581 A CN103579581 A CN 103579581A CN 201310536673 A CN201310536673 A CN 201310536673A CN 103579581 A CN103579581 A CN 103579581A
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source
porous
preparation
monocrystalline
monocrystal
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陈玉喜
郑娜
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Hunan University
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide (Fe2O3)
    • 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 relates to a functional monocrystalline porous iron oxide Fe2O3 powder material and a preparation method thereof. Fe2O3 particles are monocrystalline and porous, and an average aperture can be adjusted from meso pores to macro pores by changing process conditions. The preparation method comprises the following steps of dissolving an iron source and a fluorine source into de-ionized water according to a certain molar ratio while uniformly stirring respectively, and adding dropwise a solution of the fluorine source into a solution of the iron source; and performing a hydrothermal reaction on a mixed solution, and cooling the mixed solution to obtain the monocrystalline porous iron oxide Fe2O3 powder material. According to the monocrystalline porous iron oxide Fe2O3 powder material and the preparation method thereof, a preparation process is simple, the monocrystalline porous iron oxide Fe2O3 powder material is easy to industrially produce, and has high charging and discharging cycle performance when being used as a negative electrode material for a lithium ion battery, and the requirements of the negative electrode material for the lithium ion battery can be met.

Description

Monocrystalline porous ferric oxide powder body material and preparation method thereof
Technical field
The present invention relates to a kind of preparation method of functional material, particularly lithium ion battery anode active material iron oxide Fe 2o 3powder body material and preparation method thereof.
Background technology
In recent years, along with the fast development of smart mobile phone, notebook and electric automobile, as the capacity of the lithium ion battery of power supply, be more and more difficult to meet the demands.At present, the negative active core-shell material of commercial Li-ion battery is to adopt various graphite carbon materials, but its specific capacity only has 370 mAh/g.Iron oxide Fe 2o 3as the specific capacity of lithium ion battery negative material, up to 1000 mAh/g, approach three times of graphite material specific capacity.In addition, iron oxide is cheap, reserves are abundant and environmental friendliness, therefore becomes one of choice of cathode material for high capacity lithium ion battery of new generation.But ferric oxide powder is applied to lithium ion battery and has a larger shortcoming, and its change in volume can reach 80% in charging and discharging process, therefore easily cause ferric oxide powder and collector unsticking, thereby cause lithium ion battery to lose efficacy.
In order to reduce Fe 2o 3change in volume in charge and discharge process, document Iron oxide porous nanorods with different textural properties and surface composition:Preparation, characterization and electrochemical lithium storage capabilities, Pedro Tartaj, Jose M. Amarilla, Journal of Power Sources 196 (2011) 2164-2170 disclose a kind of method of preparing porous ferric oxide, by SiO 2coated FeOOH at high temperature heats, and then utilizes KOH to dissolve SiO 2coating layer, has finally obtained the Fe of porous 2o 3.This preparation method's complex process, long flow path, and aperture cannot regulate.
Summary of the invention
The present invention aims to provide a kind of monocrystalline porous ferric oxide Fe that utilizes inorganic anion to prepare 2o 3powder body material, and the preparation method that a kind of technique is simple, be easy to suitability for industrialized production is provided.
The present invention realizes by following scheme:
A kind of monocrystalline porous ferric oxide Fe 2o 3powder body material, each powder granule is monocrystal and is cellular.By regulating pore creating material-inorganic anion F ?content, Fe 2o 3intragranular aperture is adjusted to the macropore of average 100 nanometers from the mesopore of average approximately 10 nanometers.
A kind ofly prepare above-mentioned monocrystalline porous ferric oxide Fe 2o 3the method of powder body material, is dissolved in source of iron and fluorine source respectively in deionized water according to certain mol proportion, after fully stirring, fluorine source solution is splashed in source of iron solution, wherein Fe in source of iron and fluorine source 3+and F ?mol ratio be 1:1 ~ 1:15, then by above-mentioned through well-beaten mixed solution 100 oc ~ 200 oCbetween carry out hydro-thermal reaction 1 ~ 5 hour, last cool to room temperature.
Source of iron generally adopts Fe (NO 3) 3, Fe 2(SO 4) 3; Fluorine source generally adopts NaF, KF.
In order to prepare the monocrystalline porous oxidation iron powder body of function admirable, described source of iron and fluorine source add the preferred 1:5 ~ 1:10 of molar ratio.
Compared with prior art, the present invention possesses following advantage:
1. material of the present invention is a kind of porous ferric oxide Fe of monocrystal 2o 3powder body material, hole has higher mechanical strength, is difficult for subsiding.Meanwhile, the average-size in hole can be adjusted to from the mesopore of 10 nanometer left and right the macropore of 100 nanometer left and right.
2. adopt monocrystal porous ferric oxide Fe of the present invention 2o 3lithium ion battery prepared by powder body material possesses good charge-discharge performance.
3. preparation method's condition of the present invention is moderate, and technological process is simple.
accompanying drawing explanation
Fig. 1 (a) and (b) be respectively and utilize Fe (NO 3) 3the nanoscale Fe obtaining 2o 3the stereoscan photograph of powder body material and X-ray diffraction spectrum.
Fig. 2 nanoscale Fe 2o 3(a) N of powder body material 2isothermal adsorption desorption curve, (b) graph of pore diameter distribution.
Fig. 3 utilizes Fe (NO 3) 3the monocrystalline porous Fe that-NaF obtains 2o 3(a) stereoscan photograph of powder body material, (b) X-ray diffraction spectrum and (c) transmission electron microscope selected area electron diffraction spectrum.
Fig. 4 utilizes Fe (NO 3) 3the monocrystalline porous Fe that-NaF obtains 2o 3(a) N of powder body material 2isothermal adsorption desorption curve and (b) graph of pore diameter distribution.
Fig. 5 utilizes Fe (NO 3) 3the monocrystalline porous Fe that-NaF obtains 2o 3(a) voltage-specific capacity curve of powder body material and (b) cycle performance figure.
Fig. 6 utilizes Fe 2(SO 4) 3the monocrystalline porous Fe that-KF obtains 2o 3(a) stereoscan photograph of powder body material, (b) X-ray diffraction spectrum and (c) transmission electron microscope selected area electron diffraction spectrum.
Fig. 7 utilizes Fe 2(SO 4) 3the monocrystalline porous Fe that-KF obtains 2o 3(a) N of powder body material 2isothermal adsorption desorption curve and (b) graph of pore diameter distribution.
Fig. 8 utilizes Fe 2(SO 4) 3the monocrystalline porous Fe that-KF obtains 2o 3(a) voltage-specific capacity curve of powder body material and (b) cycle performance figure.
Embodiment
embodiment 1
According to the concentration configuration Fe (NO of 0.05 mol/L 3) 3solution is put into self-styled reactor, 100 after abundant stirring oc constant temperature 5 hours, cool to room temperature then, through the cyclic washing of deionized water and alcohol, and 100 oc vacuumize 10 hours.
Fig. 1 (a) is the stereoscan photograph of product, and product is graininess, size approximately 50 nanometers.Fig. 1 (b) is the X ray diffracting spectrum of product, and proved response product is Fe 2o 3.Fig. 2 (a) and (b) be respectively Fe 2o 3the N of powder body material 2isothermal adsorption desorption curve and the pore size distribution curve calculating according to BJH method.As can be seen from the figure, at Fe 2o 3in powder granule, there is the micropore (aperture is less than 2 nanometers) of some.
embodiment 2
By source of iron Fe (NO 3) 3, fluorine source NaF is according to Fe 3+and F ?molar concentration rate 1:5 be dissolved in separately and in deionized water, be configured to solution, after fully stirring, NaF solution is slowly splashed into Fe (NO 3) 3in solution, mixed solution is through fully stirring and move into self-styled reactor, in 150 oc constant temperature 4 hours, cool to room temperature then, through the cyclic washing of deionized water and alcohol, and 100 oc vacuumize 10 hours.Through said method, prepare monocrystalline porous Fe 2o 3powder body material is prepared into lithium ion experimental button cell as the negative active core-shell material of lithium ion battery, tests its performance.Fig. 3 (a) is the stereoscan photograph of product powder body material, and its particle size reaches micron order, and the X-ray diffraction spectrum of Fig. 3 (b) has proved that it is for Fe 2o 3.The transmission electron microscope selected area electron diffraction of Fig. 3 (c) shows, each micron-sized particle is monocrystal, but not the secondary aggregate of nano particle.Fig. 4 (a) and (b) be respectively Fe 2o 3the N of powder 2isothermal adsorption desorption curve and the pore size distribution curve calculating according to BJH method.As can be seen from Figure, at micron-sized monocrystal Fe 2o 3granule interior exists a certain amount of mesoporous, and the size in hole is in 10 nanometer left and right.Fig. 5 (a) and (b) be respectively above-mentioned monocrystalline porous Fe 2o 3voltage-specific capacity curve of powder body material and cycle performance figure.As can be seen from the figure, as high energy lithium ion cell negative material, this monocrystalline porous Fe 2o 3powder body material has better charge-discharge performance, its first embedding lithium/de-lithium specific capacity respectively up to 1012/833 mAh/g, approach three times of graphite negative electrodes material specific capacity.Meanwhile, this monocrystalline porous Fe 2o 3powder body material has better cycle performance, and its de-lithium specific capacity is along with the increase of cycle-index presents the trend that first declines and rise afterwards.
embodiment 3
By source of iron Fe 2(SO 4) 3, fluorine source KF is according to Fe 3+and F ?molar concentration rate 1:10 be dissolved in separately and in deionized water, be configured to solution, after fully stirring, KF solution is slowly splashed into Fe 2(SO 4) 3in solution, mixed solution is through fully stirring and move into self-styled reactor, in 200 oc constant temperature 1 hour, cool to room temperature then, through the cyclic washing of deionized water and alcohol, and 100 oc vacuumize 10 hours.Through said method, prepare monocrystalline porous Fe 2o 3powder body material is prepared into lithium ion experimental button cell as the negative active core-shell material of lithium ion battery, tests its performance.Fig. 6 (a) is the stereoscan photograph of product, can find out, these product present cellular, and particle size reaches micron order.Fig. 6 (b) is the X-ray diffraction spectrum of product, proves that it is Fe 2o 3.The transmission electron microscope selected area electron diffraction of Fig. 6 (c) shows, each micron-sized particle is monocrystal, and therefore this product is monocrystalline porous Fe 2o 3powder body material.Fig. 7 (a) and (b) be respectively monocrystalline porous Fe 2o 3the N of powder 2isothermal adsorption desorption curve and the pore size distribution curve calculating according to BJH method.As can be seen from Figure, at micron-sized monocrystal Fe 2o 3except there is a certain amount of a large amount of macropore of main existence 10 about nanometers mesoporous that is of a size of in granule interior, the size in hole is in 100 nanometers left and right.Fig. 8 (a) is this monocrystalline porous Fe 2o 3voltage-specific capacity curve of powder, its first embedding lithium/de-lithium specific capacity respectively up to 1420/1170 mAh/g, surpass three times of graphite negative electrodes material specific capacity.Fig. 8 (b) is the charge-discharge performance figure of above-mentioned material, and as can be seen from Figure, the charge-discharge performance of material is more stable, and the reversible de-lithium capacity after 50 circulations is 1067 mAh/g, and reversible capacity conservation rate has reached 91%, this monocrystalline porous Fe 2o 3powder body material has better charge-discharge performance.

Claims (4)

1. a functional monocrystal porous ferric oxide Fe 2o 3powder body material, is characterized in that: each Fe 2o 3powder granule is monocrystal, and monocrystal Fe 2o 3particle is cellular; By changing preparation condition, average pore size can be adjusted to 100 nanometers by 10 nanometers.
2. prepare functional monocrystal porous Fe as claimed in claim 1 for one kind 2o 3the method of powder body material, is characterized in that: source of iron and fluorine source are dissolved in respectively in deionized water and are stirred, then fluorine source solution is splashed in source of iron solution and stirred, wherein Fe in source of iron and fluorine source 3+and F ?mol ratio be 1:1 ~ 1:15, then above-mentioned mixed solution is carried out to hydro-thermal reaction, reaction temperature is 100 oc ~ 200 oc, the reaction time is 1 ~ 5 hour, last cool to room temperature.
3. the functional monocrystal porous Fe of preparation as claimed in claim 2 2o 3the method of powder body material, is characterized in that: the additional proportion in described source of iron and fluorine source is preferred: 1:2≤Fe 3+: F ?mol ratio≤1:10.
4. prepare as claimed in claim 2 or claim 3 functional monocrystal Fe 2o 3the method of porous powder material, is characterized in that: the temperature of described hydro-thermal reaction preferably 120 oc ~ 180 oc.
CN201310536673.4A 2013-07-23 2013-11-04 Monocrystalline porous iron oxide powder material and preparation method thereof Pending CN103579581A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104966839A (en) * 2015-07-15 2015-10-07 山东大学 Lithium battery negative electrode material modifying method
CN105220221A (en) * 2015-11-12 2016-01-06 华东理工大学 A kind of preparation method of mesoporous single crystals ferric oxide and photoelectrochemistry water splitting device thereof
CN110371924A (en) * 2019-07-25 2019-10-25 许昌学院 A kind of Fe2O3Porous nano line electrode material, preparation method and application
WO2020253843A1 (en) * 2019-06-21 2020-12-24 中国科学院上海硅酸盐研究所 A class of porous metal oxide based electrochemical energy storage materials, preparation method therefor and use thereof

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US3466234A (en) * 1966-06-20 1969-09-09 Canadian Patents Dev Electrolytic formation of films of fe2o3
CN101037232A (en) * 2007-04-26 2007-09-19 安徽工业大学 Method for preparing radius-controllable ferric oxide hollow ball
CN101468817A (en) * 2007-12-25 2009-07-01 中国科学院过程工程研究所 Mesoporous nanocrystalline assembled porous bengala microsphere and preparation thereof
CN101555624A (en) * 2009-05-06 2009-10-14 新疆大学 Synthetic method for uniform mono-dispersion Alpha-Fe2O3 single chip

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US3466234A (en) * 1966-06-20 1969-09-09 Canadian Patents Dev Electrolytic formation of films of fe2o3
CN101037232A (en) * 2007-04-26 2007-09-19 安徽工业大学 Method for preparing radius-controllable ferric oxide hollow ball
CN101468817A (en) * 2007-12-25 2009-07-01 中国科学院过程工程研究所 Mesoporous nanocrystalline assembled porous bengala microsphere and preparation thereof
CN101555624A (en) * 2009-05-06 2009-10-14 新疆大学 Synthetic method for uniform mono-dispersion Alpha-Fe2O3 single chip

Non-Patent Citations (1)

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Title
郑娜: "多孔α-Fe2O3的结构调控即电化学性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅱ辑》, no. 06, 15 June 2013 (2013-06-15) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104966839A (en) * 2015-07-15 2015-10-07 山东大学 Lithium battery negative electrode material modifying method
CN105220221A (en) * 2015-11-12 2016-01-06 华东理工大学 A kind of preparation method of mesoporous single crystals ferric oxide and photoelectrochemistry water splitting device thereof
CN105220221B (en) * 2015-11-12 2018-06-19 华东理工大学 A kind of preparation method of mesoporous single crystals iron oxide and its optical electro-chemistry water splitting device
WO2020253843A1 (en) * 2019-06-21 2020-12-24 中国科学院上海硅酸盐研究所 A class of porous metal oxide based electrochemical energy storage materials, preparation method therefor and use thereof
CN110371924A (en) * 2019-07-25 2019-10-25 许昌学院 A kind of Fe2O3Porous nano line electrode material, preparation method and application
CN110371924B (en) * 2019-07-25 2022-06-14 许昌学院 Fe2O3 porous nanowire electrode material, preparation method and application

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Application publication date: 20140212