CN106186082B - A kind of Fe2O3The Fe of phase transformation synthesis3O4Hallow nanoparticles and its application - Google Patents

A kind of Fe2O3The Fe of phase transformation synthesis3O4Hallow nanoparticles and its application Download PDF

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Publication number
CN106186082B
CN106186082B CN201610593930.1A CN201610593930A CN106186082B CN 106186082 B CN106186082 B CN 106186082B CN 201610593930 A CN201610593930 A CN 201610593930A CN 106186082 B CN106186082 B CN 106186082B
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nanoparticles
hallow nanoparticles
phase transformation
hallow
sodium
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CN106186082A (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 its application in sodium-ion battery.The Fe3O4Hallow nanoparticles are that iron chloride and terephthalic acid (TPA) is dissolved into N, in N dimethylformamides, then instill sodium hydroxide and stir and evenly mix, be then transferred in reactor and reacted, red Fe is obtained through centrifuge washing2O3Hallow nanoparticles, finally phase transformation is made after high annealing under argon atmosphere.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 show excellent storage sodium performance, can be used as anode material of lithium-ion battery.

Description

A kind of Fe2O3The Fe of phase transformation synthesis3O4Hallow nanoparticles and its application
Technical field
The invention belongs to electrode material technical field, and in particular to a kind of Fe2O3The Fe of phase transformation synthesis3O4Hollow Nano grain Son and its application.
Background technology
Lithium ion battery（LIBs）Due to high power capacity, high voltage and the remarkable advantage such as having extended cycle life and extensively should For fields such as mobile electronic device, national defense industry, electric automobiles.But with the continuous popularization of lithium ion battery, lithium（Carbonic acid Lithium）Price constantly rise, and there is also reserves in the earth are less, skewness, are difficult to the problems such as exploitation for lithium resource.Sodium element For lithium, reserves are more rich, cheap and wide material sources, thus sodium-ion battery is widely closed in recent years Note, future have application prospect more more preferable than LIBs in the large-scale application in energy storage field.But sodium-ion battery is due to a lack of conjunction Suitable negative material and restrict its practical application, therefore, the anode material of lithium-ion battery for developing excellent performance is the current neck The study hotspot and emphasis in domain.
The content of the invention
It is an object of the invention to provide a kind of Fe2O3The Fe of phase transformation synthesis3O4Hallow nanoparticles and its application, gained Fe3O4Hallow nanoparticles show excellent storage sodium performance, negative material can be used as, for preparing sodium-ion battery.
To achieve the above object, the present invention adopts the following technical scheme that：
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 Terephthalic acid (TPA) is dissolved into 8-10 mL DMFs, and 1-4 mL 0.1-0.5 mol/L are instilled after stirring and evenly mixing Sodium hydroxide, continue to stir 10-20 min, 3-12h is then reacted in 130-170 DEG C of reactor, reactant is through centrifuge washing Obtain red product, as Fe2O3Hallow nanoparticles；Gained Fe2O3Hallow nanoparticles are under argon atmosphere, through 300-500 DEG C Phase transformation generates the Fe after annealing3O4Hallow nanoparticles.
Gained Fe3O4Hallow nanoparticles can be used as negative material, for preparing sodium-ion battery.
The remarkable advantage of the present invention is：
The ingenious application of this method participates in the organic ligand of reaction, with Fe3+The metal that coordination combines to form transition state is organic Compound, then, process of the metal organic complexes through dissolving recrystallization, form Fe2O3Hallow nanoparticles presoma, then Reduction obtains Fe under argon atmosphere3O4Hallow nanoparticles.
Present invention preparation cost is low, and product purity is high, excellent performance, and can largely synthesize.Prepared Fe3O4It is hollow to receive Rice corpuscles shows of a relatively high specific capacity and good cyclical stability in sodium-ion battery, is iron-based electrode material Design and application provide good method and guidance.
Brief description of the drawings
Fig. 1 is Fe2O3Hallow nanoparticles presoma and Fe3O4The XRD of hallow nanoparticles.
Fig. 2 is Fe3O4The scanning electron microscope (SEM) photograph of hallow nanoparticles（a）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.
Embodiment
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 Terephthalic acid (TPA) is dissolved into 8-10 mL DMFs, and 1-4 mL 0.1-0.5 mol/L are instilled after stirring and evenly mixing Sodium hydroxide, continue to stir 10-20 min, 3-12h is then reacted in 130-170 DEG C of reactor, reactant is through centrifuge washing Obtain red product, as Fe2O3Hallow nanoparticles；Gained Fe2O3Hallow nanoparticles are under argon atmosphere, through 300-500 DEG C Phase transformation generates the Fe after annealing3O4Hallow nanoparticles.
In order that content of the present invention easily facilitates understanding, with reference to embodiment 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 terephthalic acid (TPA)s are dissolved into 8 mL DMFs, stirred and evenly mixed After instill the mol/L sodium hydroxides of 1 mL 0.1, continue stir 10 min, 12h, reactant are then reacted in 130 DEG C of reactors Red product, as Fe are obtained through centrifuge washing2O3Hallow nanoparticles；Gained Fe2O3Hallow nanoparticles under argon atmosphere, Phase transformation generates the Fe after 300 DEG C of annealing3O4Hallow nanoparticles.
Embodiment 2
0.2 g iron chloride and 0.3 g terephthalic acid (TPA)s are dissolved into 9 mL DMFs, stirred and evenly mixed After instill the mol/L sodium hydroxides of 2 mL 0.2, continue stir 15 min, 8h, reactant are then reacted in 150 DEG C of reactors Red product, as Fe are obtained through centrifuge washing2O3Hallow nanoparticles；Gained Fe2O3Hallow nanoparticles under argon atmosphere, Phase transformation generates the Fe after 400 DEG C of annealing3O4Hallow nanoparticles.
Embodiment 3
0.4 g iron chloride and 0.6 g terephthalic acid (TPA)s are dissolved into 10 mL DMFs, stirred and evenly mixed After instill the mol/L sodium hydroxides of 4 mL 0.5, continue stir 20 min, 3h, reactant are then reacted in 170 DEG C of reactors Red product, as Fe are obtained through centrifuge washing2O3Hallow nanoparticles；Gained Fe2O3Hallow nanoparticles under argon atmosphere, Phase transformation generates the Fe after 500 DEG C of annealing3O4Hallow nanoparticles.
Fig. 1 is Fe2O3Hallow nanoparticles presoma and Fe3O4The XRD of hallow nanoparticles.Can from Fig. 1 Go out, gained Fe2O3Hallow nanoparticles presoma is pure phase rhomboidal crystal, gained Fe3O4Hallow nanoparticles are pure phase cubic crystal Body.
Fig. 2 is Fe3O4The scanning electron microscope (SEM) photograph of hallow nanoparticles（a）And transmission electron microscope picture（b）.From figure 2 it can be seen that Gained Fe3O4Nano-particle is internally hollow structure, and its overall particle diameter is and big by many sizes between 100-200 nm About 15-20 nm small particles composition.
With prepared Fe3O4Nano-particle is measured as anode material of lithium-ion battery.Sodium-ion battery assembles： Fe3O4Nano-particle：Kynoar：Acetylene black=80-85：5-10：1.2 cm are equably coated in after 10-15 mixed grindings2's Negative pole is done on copper sheet, just extremely metallic sodium, electrolyte are 1M NaClO4EC+DEC (EC/ DEC=1/1 v/v) solution.Electricity Pond is assembled in the lower glove box of argon gas protection and carried out（Oxygen and moisture are below 1ppm）.
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 ramp type charging and discharging curve, without obvious voltage platform；It is close in the electric current that current density is 100 mA/g Under degree, discharge capacity is up to 442 mAh/g first for it, and initial charge capacity is up to 221 mAh/g.
Fig. 4 is Fe3O4With Fe2O3The cycle performance comparison diagram of hallow nanoparticles.Figure 4, it is seen that Fe2O3Although With higher discharge capacity first（686 mAh/g）, but then its capacity declines rapidly, after 60 circulations, its capacity Only 15 mAh/g；And Fe3O4After 60 circulations, its reversible specific capacity is still stablized in 150 mAh/g.
As can be seen here, with Fe2O3Nano-particle is compared, Fe3O4Nano-particle 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 equivalent changes done according to scope of the present invention patent with Modification, it should all belong to the covering scope of the present invention.

Claims (1)

  1. A kind of 1. Fe2O3Phase transformation synthesizes Fe3O4The method of hallow nanoparticles, it is characterised in that：By 0.1-0.4 g iron chloride and 0.1-0.6 g terephthalic acid (TPA)s are dissolved into 8-10 mL DMFs, and 1-4 mL 0.1- are instilled after stirring and evenly mixing 0.5 mol/L sodium hydroxides, continue to stir 10-20 min, 3-12h is then reacted in 130-170 DEG C, reactant is washed through centrifugation Wash to obtain Fe2O3Hallow nanoparticles；Gained Fe2O3Hallow nanoparticles are under argon atmosphere, the phase transformation after 300-500 DEG C of annealing Generate the Fe3O4Hallow nanoparticles.
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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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
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
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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