CN106186082A - A kind of Fe2o3the Fe of phase transformation synthesis3o4hallow nanoparticles and application thereof - Google Patents

A kind of Fe2o3the Fe of phase transformation synthesis3o4hallow nanoparticles and application thereof Download PDF

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Publication number
CN106186082A
CN106186082A CN201610593930.1A CN201610593930A CN106186082A CN 106186082 A CN106186082 A CN 106186082A CN 201610593930 A CN201610593930 A CN 201610593930A CN 106186082 A CN106186082 A CN 106186082A
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nanoparticles
hallow nanoparticles
phase transformation
hallow
sodium
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CN106186082B (en
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洪振生
周凯强
真义超
黄志高
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Fujian Normal University
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Fujian Normal University
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    • 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
    • C01G49/08—Ferroso-ferric oxide (Fe3O4)
    • 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
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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 a kind of Fe2O3The Fe of phase transformation synthesis3O4Hallow nanoparticles and the application in sodium-ion battery thereof.Described Fe3O4Hallow nanoparticles is iron chloride and p-phthalic acid to be dissolved in N, N dimethylformamide, then instills sodium hydroxide stirring and evenly mixing, is then transferred in reactor react, and washing obtains red Fe by centrifugation2O3Hallow nanoparticles, finally under argon atmosphere, after high annealing, phase transformation prepares.The present invention passes through solvent-thermal method one-step synthesis Fe2O3Hallow nanoparticles presoma, then cause Fe via heat treatment2O3Phase transformation generates Fe3O4, gained Fe3O4Hallow nanoparticles shows the storage sodium performance of excellence, can be used as anode material of lithium-ion battery.

Description

A kind of Fe2O3The Fe of phase transformation synthesis3O4Hallow nanoparticles and application thereof
Technical field
The invention belongs to electrode material technical field, be specifically related to a kind of Fe2O3The Fe of phase transformation synthesis3O4Hollow Nano grain Son and application thereof.
Background technology
Lithium ion battery (LIBs) extensively should owing to having high power capacity, high voltage and the remarkable advantage such as have extended cycle life For fields such as mobile electronic device, national defense industry, electric automobiles.But it is as the most universal of lithium ion battery, lithium (carbonic acid Lithium) price constantly rise, and lithium resource there is also that reserves in the earth are less, skewness, is difficult to the problems such as exploitation.Sodium element For lithium, reserves are more rich, cheap and wide material sources, thus sodium-ion battery is closed the most widely Note, will have more more preferable application prospect than LIBs future in the large-scale application in energy storage field.But sodium-ion battery for want of closes Suitable negative material and restrict its actual application, therefore, developing the anode material of lithium-ion battery of excellent performance is current this neck The study hotspot in territory and emphasis.
Summary of the invention
It is an object of the invention to provide a kind of Fe2O3The Fe of phase transformation synthesis3O4Hallow nanoparticles and application thereof, gained Fe3O4Hallow nanoparticles shows the storage sodium performance of excellence, can be used for preparing sodium-ion battery as negative material.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of Fe2O3The Fe of phase transformation synthesis3O4Hallow nanoparticles, it is to benzene by 0.1-0.4 g iron chloride and 0.1-0.6 g Dioctyl phthalate is dissolved in 8-10 mL DMF, instills 1-4 mL 0.1-0.5 mol/L hydrogen-oxygen after stirring and evenly mixing Changing sodium, continue stirring 10-20 min, then in 130-170 DEG C of reaction kettle for reaction 3-12h, reactant washs red by centrifugation Color product, is Fe2O3Hallow nanoparticles；Gained Fe2O3Hallow nanoparticles is under argon atmosphere, through 300-500 DEG C of annealing Rear phase transformation generates described Fe3O4Hallow nanoparticles.
Gained Fe3O4Hallow nanoparticles can be used for preparing sodium-ion battery as negative material.
The remarkable advantage of the present invention is:
The ingenious application of this method participates in the organic ligand of reaction, with Fe3+Coordination combines the metal organic composite forming transitive state Thing, then, metal organic complexes, through dissolving the process of recrystallization, forms Fe2O3Hallow nanoparticles presoma, then at argon Under atmosphere, reduction obtains Fe3O4Hallow nanoparticles.
Preparation cost of the present invention is low, and product purity is high, excellent performance, and can synthesize in a large number.Prepared Fe3O4Hollow receive Rice corpuscles shows of a relatively high specific capacity and good cyclical stability in sodium-ion battery, for iron-based electrode material Design and application provide good method and guidance.
Accompanying drawing explanation
Fig. 1 is Fe2O3Hallow nanoparticles presoma and Fe3O4The XRD figure of hallow nanoparticles.
Fig. 2 is Fe3O4The scanning electron microscope (SEM) photograph (a) of hallow nanoparticles and transmission electron microscope picture (b).
Fig. 3 is Fe3O4The charging and discharging curve figure of hallow nanoparticles.
Fig. 4 is Fe3O4With Fe2O3The cycle performance comparison diagram of hallow nanoparticles.
Detailed description of the invention
A kind of Fe2O3The Fe of phase transformation synthesis3O4Hallow nanoparticles, it is by 0.1-0.4 g iron chloride and 0.1-0.6 g P-phthalic acid is dissolved in 8-10 mL DMF, instills 1-4 mL 0.1-0.5 mol/L after stirring and evenly mixing Sodium hydroxide, continues stirring 10-20 min, and then in 130-170 DEG C of reaction kettle for reaction 3-12h, reactant washs by centrifugation Obtain red product, be Fe2O3Hallow nanoparticles；Gained Fe2O3Hallow nanoparticles is under argon atmosphere, through 300-500 DEG C After annealing, phase transformation generates described Fe3O4Hallow nanoparticles.
In order to make content of the present invention easily facilitate understanding, below in conjunction with detailed description of the invention to of the present invention Technical scheme is described further, but the present invention is not limited only to this.
Embodiment 1
0.1 g iron chloride and 0.1 g p-phthalic acid are dissolved in 8 mL DMFs, drip after stirring and evenly mixing Enter 1 mL 0.1 mol/L sodium hydroxide, continue stirring 10 min, then in 130 DEG C of reaction kettle for reaction 12h, reactant through from The heart washs to obtain red product, is Fe2O3Hallow nanoparticles；Gained Fe2O3Hallow nanoparticles is under argon atmosphere, through 300 DEG C annealing after phase transformation generate described Fe3O4Hallow nanoparticles.
Embodiment 2
0.2 g iron chloride and 0.3 g p-phthalic acid are dissolved in 9 mL DMFs, drip after stirring and evenly mixing Enter 2 mL 0.2 mol/L sodium hydroxide, continue stirring 15 min, then in 150 DEG C of reaction kettle for reaction 8h, reactant through from The heart washs to obtain red product, is Fe2O3Hallow nanoparticles；Gained Fe2O3Hallow nanoparticles is under argon atmosphere, through 400 DEG C annealing after phase transformation generate described Fe3O4Hallow nanoparticles.
Embodiment 3
0.4 g iron chloride and 0.6 g p-phthalic acid are dissolved in 10 mL DMFs, drip after stirring and evenly mixing Enter 4 mL 0.5 mol/L sodium hydroxide, continue stirring 20 min, then in 170 DEG C of reaction kettle for reaction 3h, reactant through from The heart washs to obtain red product, is Fe2O3Hallow nanoparticles；Gained Fe2O3Hallow nanoparticles is under argon atmosphere, through 500 DEG C annealing after phase transformation generate described Fe3O4Hallow nanoparticles.
Fig. 1 is Fe2O3Hallow nanoparticles presoma and Fe3O4The XRD figure of hallow nanoparticles.Can from Fig. 1 Go out, gained Fe2O3Hallow nanoparticles presoma is pure phase rhomboidal crystal, gained Fe3O4Hallow nanoparticles is pure phase cubic crystal Body.
Fig. 2 is Fe3O4The scanning electron microscope (SEM) photograph (a) of hallow nanoparticles and transmission electron microscope picture (b).From figure 2 it can be seen that Gained Fe3O4Nanoparticle be internally hollow structure, its overall particle diameter is between 100-200 nm, and big by many sizes It is about the small particles composition of 15-20 nm.
With prepared Fe3O4Nanoparticle is measured as anode material of lithium-ion battery.Sodium-ion battery assembles: Fe3O4Nanoparticle: Kynoar: be coated in 1.2 cm equably after acetylene black=80-85:5-10:10-15 mixed grinding2's Doing negative pole, the most extremely metallic sodium on copper sheet, electrolyte is 1M NaClO4EC+DEC (EC/ DEC=1/1 v/v) solution.Electricity Pond is assembled under argon shield and carries out (oxygen and moisture are below 1ppm) in glove box.
Fig. 3 is Fe3O4The charging and discharging curve figure of hallow nanoparticles.From figure 3, it can be seen that Fe3O4Hallow nanoparticles Charging and discharging curve be the charging and discharging curve of ramp type, without obvious voltage platform；Close at the electric current that electric current density is 100 mA/g Under degree, its first discharge capacity reach 442 mAh/g, initial charge capacity reaches 221 mAh/g.
Fig. 4 is Fe3O4With Fe2O3The cycle performance comparison diagram of hallow nanoparticles.Figure 4, it is seen that Fe2O3Although There is higher discharge capacity first (686 mAh/g), but its capacity declines rapidly subsequently, after 60 times circulate, its capacity Only 15 mAh/g；And Fe3O4After 60 times circulate, its reversible specific capacity is still stable at 150 mAh/g.
As can be seen here, with Fe2O3Nanoparticle is compared, Fe3O4Nanoparticle has of a relatively high specific capacity and good Cyclical stability, it is more suitable for electrode material.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with Modify, all should belong to the covering scope of the present invention.

Claims (2)

1. a Fe2O3The Fe of phase transformation synthesis3O4Hallow nanoparticles, it is characterised in that: by 0.1-0.4 g iron chloride and 0.1- 0.6 g p-phthalic acid is dissolved in 8-10 mL DMF, instills 1-4 mL 0.1-0.5 after stirring and evenly mixing Mol/L sodium hydroxide, continues stirring 10-20 min, then reacts 3-12h in 130-170 DEG C, and reactant washs by centrifugation Fe2O3Hallow nanoparticles；Gained Fe2O3Hallow nanoparticles is under argon atmosphere, and after 300-500 DEG C of annealing, phase transformation generates Described Fe3O4Hallow nanoparticles.
2. a Fe as claimed in claim 13O4Hallow nanoparticles application in sodium-ion battery.
CN201610593930.1A 2016-07-27 2016-07-27 A kind of Fe2O3The Fe of phase transformation synthesis3O4Hallow nanoparticles and its application Expired - Fee Related CN106186082B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107572595A (en) * 2017-08-17 2018-01-12 合肥国轩高科动力能源有限公司 A kind of preparation method of hollow loose structure iron oxide cathode material
CN108807882A (en) * 2018-05-24 2018-11-13 江西师范大学 A kind of Fe with porous octahedral structure2O3/Fe3O4The preparation method of@C/G composite materials
CN110078130A (en) * 2019-05-19 2019-08-02 东北电力大学 A kind of preparation method of hollow structure Fe-base compound and its application as super capacitor anode material

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US20040179997A1 (en) * 2002-10-30 2004-09-16 Council Of Scientific And Industrial Research Single-step simple and economical process for the preparation of nanosized acicular magnetic iron oxide particles of maghemite phase
CN101698516A (en) * 2009-11-06 2010-04-28 南京大学 Method for preparing hollow spherical ferroferric oxide nano material
CN104167536A (en) * 2014-07-09 2014-11-26 浙江大学 Preparation method and purpose thereof of spherical ferriferrous oxide nano particles with controllable size

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US20040179997A1 (en) * 2002-10-30 2004-09-16 Council Of Scientific And Industrial Research Single-step simple and economical process for the preparation of nanosized acicular magnetic iron oxide particles of maghemite phase
CN101698516A (en) * 2009-11-06 2010-04-28 南京大学 Method for preparing hollow spherical ferroferric oxide nano material
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107572595A (en) * 2017-08-17 2018-01-12 合肥国轩高科动力能源有限公司 A kind of preparation method of hollow loose structure iron oxide cathode material
CN108807882A (en) * 2018-05-24 2018-11-13 江西师范大学 A kind of Fe with porous octahedral structure2O3/Fe3O4The preparation method of@C/G composite materials
CN108807882B (en) * 2018-05-24 2022-04-26 江西师范大学 Fe with porous octahedral structure2O3/Fe3O4Preparation method of @ C/G composite material
CN110078130A (en) * 2019-05-19 2019-08-02 东北电力大学 A kind of preparation method of hollow structure Fe-base compound and its application as super capacitor anode material
CN110078130B (en) * 2019-05-19 2021-11-26 东北电力大学 Preparation method of hollow-structure iron-based compound and application of hollow-structure iron-based compound as cathode material of supercapacitor

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