CN103551092A - Preparation method of FeMnO3 hollow nanospheres - Google Patents

Abstract

The invention discloses a preparation method of FeMnO3 hollow nanospheres, and the preparation method comprises the following steps: (1) dissolving manganese(II) acetate tetrahydrate and iron(III) chloride hexahydrate in the molar ratio of 1:1 in absolute ethanol; (2) adding carbon nanospheres with the diameter of 100-500nm for ultrasonic dispersion; (3) with mixing, adding full dose of an ammonia aqueous solution to completely precipitate manganese ions and iron ions; (4), centrifuging and washing the precipitate, and then drying to obtain black powder; (5) calcining the black powder in the air or oxygen atmosphere at 400-800 DEG C to obtain the FeMnO3 hollow nanospheres. The new FeMnO3 hollow nanospheres can be used as an electrode material for a supercapacitor.

Description

A kind of FeMnO 3the preparation method of hollow nano-sphere

Technical field

The present invention relates to a kind of novel FeMnO ₃the preparation method of hollow nano-sphere, belongs to inorganic functional material preparing technical field.

Background technology

In recent years, Fe-Mn oxidation compound is subject to scientific worker's extensive concern, can be applicable to many sciemtifec and technical spheres, comprise magnetic memory, electrical devices, ferrofluid, catalyst, microwave and biomedicine etc., but at present the research of Fe-Mn oxidation compound is also only limited to study MnFe ₂o ₄and MnFe ₂o ₄composite construction with other metal oxide.About MnFe ₂o ₄synthetic, early stage solvent-thermal method, coprecipitation and sol-gel process, the MnFe preparing of mostly adopting ₂o ₄spherical or graininess mostly.

Inorganic hollow microspheres or nanosphere are because it has special hollow-core construction, bigger serface, little density and special mechanical property, be all with a wide range of applications in every field such as the slowly-releasing of photoelectric material, clad material, reaction engineering, medicine, dyestuff etc., chemical building materials.Template is to prepare hollow ball structure material the most extensively and effective method, and the size of template has directly determined the size of hollow ball, the advantages such as that template has is predictable, product form homogeneous, repeatability.

FeMnO ₃a kind of brand-new Fe-Mn oxidation compound, the synthetic method of so far there are no such special appearance material of bibliographical information.

Summary of the invention

The object of this invention is to provide that a kind of reaction temperature is low, repeatability is high, technique is simple and eco-friendly novel FeMnO ₃the preparation method of hollow nano-sphere.

Implementation procedure of the present invention is as follows:

A kind of FeMnO ₃the preparation method of hollow nano-sphere, comprises the following steps:

(1) the four hydration manganese acetates and the Iron(III) chloride hexahydrate that by mol ratio, are 1:1 are dissolved in absolute ethyl alcohol;

(2) adding diameter is the nano carbon microsphere of 100～500nm, ultrasonic dispersion;

(3) under stirring, add enough ammonia spirits that manganese ion and iron ion are precipitated completely;

(4) the dry black powder that to obtain after centrifugal, washing precipitation;

(5) black powder 400～800 ℃ of calcinings under oxygen or air atmosphere obtain FeMnO ₃hollow nano-sphere.

In above-mentioned steps (2), nano carbon microsphere adopts glucose hydro-thermal legal system for obtaining, and specifically, 4g glucose is dissolved in 42ml distilled water, be transferred in the autoclave of inner liner polytetrafluoroethylene, 180 ℃ of reaction 10h are centrifugal, washing, dries, and obtains nano carbon microsphere.Nanometer is concepts of scale in this case, is not limited to below 100nm.

In above-mentioned steps (2), the quality mol ratio of the nano carbon microsphere adding and four hydration manganese acetates is 1:(0.5～2) g/mmol.

FeMnO prepared by the present invention ₃hollow nano-sphere can be used as electrode material for super capacitor.

Advantage of the present invention and good effect: the present invention adopts a kind of sacrifice template to prepare novel FeMnO ₃hollow nano-sphere, technique is simply controlled, environmental friendliness, synthetic product pattern homogeneous, Size Distribution narrow range, specific area are large.This novel FeMnO ₃hollow nano-sphere can be used as the electrode material of ultracapacitor, in thermal energy storage process, electrochemical reaction has occurred, and has produced Faraday pseudo-capacitance, has improved its specific capacity.

Accompanying drawing explanation

The FeMnO that under Fig. 1 different temperatures, calcining obtains ₃the XRD collection of illustrative plates of hollow nano-sphere;

At 500 ℃ of Fig. 2, calcine the FeMnO that 5h makes ₃the SEM photo of hollow nano-sphere;

Under Fig. 3 different temperatures, calcine the FeMnO that 5h makes ₃the TEM photo of hollow nano-sphere;

Under Fig. 4 different temperatures, calcine the FeMnO that 5h makes ₃cyclic voltammetric (CV) curve of hollow nano-sphere under different sweep speeds;

At 500 ℃ of Fig. 5, calcine the FeMnO that 5h makes ₃the curve that hollow nano-sphere changes with cycle-index than electric capacity.

The specific embodiment

The preparation of nano carbon microsphere template: 4g glucose is dissolved in 42ml distilled water, is transferred in the autoclave of inner liner polytetrafluoroethylene, 180 ℃ of reaction 10h, centrifugal, washing, dries, and obtains nano carbon microsphere.

FeMnO of the present invention ₃the preparation method of hollow nano-sphere, comprises the following steps:

(1) Iron(III) chloride hexahydrate of the four hydration manganese acetates of 0.5mmol and 0.5mmol is dissolved in the absolute ethyl alcohol of 10ml;

(2) 0.5g nano carbon microsphere is added in the mixed solution of step (1) to ultrasonic being uniformly dispersed;

(3) ethanolic solution that 5ml is contained to 0.5ml concentrated ammonia liquor dropwise joins in the suspension obtaining in step (2), stirs it is evenly mixed;

(4) under room temperature after standing 3h, centrifugation, water and absolute ethyl alcohol respectively wash three times, and the solid obtaining is dry at 60 ℃;

(5) sample after drying is put into Muffle furnace, from room temperature, with the heating rate of 1 ℃/min, rise to respectively 400 ℃, 500 ℃ and 650 ℃ keep 5h, naturally lower the temperature, and are cooled to room temperature, obtain FeMnO ₃hollow nano-sphere.

Embodiment 1

Step 1: under room temperature, take respectively the four hydration manganese acetates of 0.5mmol and the Iron(III) chloride hexahydrate of 0.5mmol is dissolved in the ethanol solution of 10ml completely under magnetic agitation;

Step 2: 0.5g nano carbon microsphere is added in the mixed solution of step 1 to ultrasonic dispersion;

Step 3, the ethanolic solution that 5ml is contained to 0.5ml ammoniacal liquor dropwise joins in the suspension that step 2 obtains, and is uniformly mixed;

Step 4: under room temperature after standing 3h, centrifugation, water and absolute ethyl alcohol respectively wash three times, and the solid obtaining is dry at 60 ℃;

Step 5: the sample after drying is put into Muffle furnace, from room temperature, rise to 400 ℃ keep 5h with the heating rate of 1 ℃/min, cooling, is cooled to room temperature naturally, and it is to be measured that taking-up packs sample sack into.

Embodiment 2

Step 1: under room temperature, take respectively the four hydration manganese acetates of 0.5mmol and the Iron(III) chloride hexahydrate of 0.5mmol is dissolved in the ethanol solution of 10ml completely under magnetic agitation;

Step 2: 0.5g nano carbon microsphere is added in the mixed solution of step 1 to ultrasonic dispersion;

Step 3, the ethanolic solution that 5ml is contained to 0.5ml ammoniacal liquor dropwise joins in the suspension obtaining in step 2, is uniformly mixed;

Step 4: under room temperature after standing 3h, centrifugation, water and absolute ethyl alcohol respectively wash three times, and the solid obtaining is dry at 60 ℃;

Step 5: the sample after drying is put into Muffle furnace, from room temperature, rise to 500 ℃ keep 5h with the heating rate of 1 ℃/min, cooling, is cooled to room temperature naturally, and it is to be measured that taking-up packs sample sack into.

Embodiment 3

Step 1: under room temperature, take respectively the four hydration manganese acetates of 0.5mmol and the Iron(III) chloride hexahydrate of 0.5mmol is dissolved in the ethanol solution of 10ml completely under magnetic agitation;

Step 2: 0.5g nano carbon microsphere is added in the mixed solution of step 1 to ultrasonic dispersion;

Step 3, the ethanolic solution that 5ml is contained to 0.5ml ammoniacal liquor dropwise joins in the suspension obtaining in step 2, is uniformly mixed;

Step 4: under room temperature after standing 3h, centrifugation, water and absolute ethyl alcohol respectively wash three times, and the solid obtaining is dry at 60 ℃;

Step 5: the sample after drying is put into Muffle furnace, from room temperature, rise to 650 ℃ keep 5h with the heating rate of 1 ℃/min, cooling, is cooled to room temperature naturally, and it is to be measured that taking-up packs sample sack into.

Embodiment 4

The FeMnO that embodiment 1-3 is prepared ₃hollow nano-sphere carries out relevant characterization.

The FeMnO that Fig. 1 makes at different temperature lower calcination 5h ₃the XRD collection of illustrative plates of hollow nano-sphere, can find out the rising along with calcining heat, FeMnO ₃degree of crystallinity uprise;

Fig. 2 calcines the FeMnO that 5h makes at 500 ℃ ₃the field emission scanning electron microscope of hollow nano-sphere (SEM) photo, can find out the FeMnO arriving at this temperature ₃nanosphere, size all between 100-200nm, even size distribution;

The FeMnO that Fig. 3 makes at different temperature lower calcination 5h ₃the transmission electron microscope of hollow nano-sphere (TEM) photo (a is 400 ℃, and c is 500 ℃, and e is 650 ℃) and high resolution electron microscope (HRTEM) photo, can find out from TEM the FeMnO obtaining 400 ℃, 500 ℃ conditions ₃nanosphere is all hollow-core constructions, and size is at 100--200nm, the FeMnO obtaining under 650 ℃ of conditions ₃for graininess.From HRTEM, can find out, along with the rising of calcining heat, FeMnO ₃the lattice fringe on nanosphere surface is obvious gradually, and crystallization degree is high, consistent with the test result of XRD;

The FeMnO that adopts embodiment 1 to 3 to prepare ₃under three electrode simulated systems, test that its ultracapacitor electrochemical properties the results are shown in Figure 4, Fig. 5.

Step 1: by FeMnO ₃, acetylene black, PVDF(0.02g/ml) in mass ratio the ratio of 8:1:1 in agate mortar, mix, add absolute ethyl alcohol fully to grind;

Step 2: take the quality of the nickel foam of 1 * 1.5cm, then repeatedly dip in above-mentioned mixed liquor, until obtain appropriate mass;

Step 3: will be moistened with nickel foam vacuum drying 12h at 120 ℃ of mixed liquor, weigh compressing tablet;

Step 4: the foam nickel electrode of above-mentioned preparation of take is working electrode, and saturated calomel electrode is reference electrode, and Pt plate electrode is to electrode, the KOH of 2M of take is electrolyte, carries out electro-chemical test on CHI660B electrochemical workstation.

The FeMnO that Fig. 4 makes at different temperature lower calcination 5h ₃cyclic voltammetric (CV) curve (a be 400 ℃, b be 500 ℃, c be 650 ℃) of hollow nano-sphere under different sweep speeds.From its CV curve, can find out all generation redox reactions that obtain of three temperature, produce Faraday pseudo-capacitance.Fig. 4 (d) is the ratio capacitance variations of three samples under different scanning rates;

Fig. 5 calcines the FeMnO that 5h makes at 500 ℃ ₃the curve (a) that the ratio electric capacity that hollow nano-sphere obtains every 100 GCD circulations changes with cycle-index, the contrast (b) of 1-3,501-503, the lower GCD curve of 1001-1003 circulation, current density is 1A/g.

Claims (6)

1. a FeMnO ₃the preparation method of hollow nano-sphere, is characterized in that comprising the following steps:

(1) the four hydration manganese acetates and the Iron(III) chloride hexahydrate that by mol ratio, are 1:1 are dissolved in absolute ethyl alcohol;

(2) adding diameter is the nano carbon microsphere of 100～500nm, ultrasonic dispersion;

(3) under stirring, add enough ammonia spirits that manganese ion and iron ion are precipitated completely;

(4) the dry black powder that to obtain after centrifugal, washing precipitation;

(5) black powder 400～800 ℃ of calcinings under oxygen or air atmosphere obtain FeMnO ₃hollow nano-sphere.

2. FeMnO according to claim 1 ₃the preparation method of hollow nano-sphere, is characterized in that: the described nano carbon microsphere of step (2) adopts glucose hydro-thermal legal system for obtaining.

3. FeMnO according to claim 2 ₃the preparation method of hollow nano-sphere, is characterized in that: 4g glucose is dissolved in 42ml distilled water, is transferred in the autoclave of inner liner polytetrafluoroethylene, and 180 ℃ of reaction 10h, centrifugal, washing, dries, and obtains nano carbon microsphere.

4. FeMnO according to claim 1 ₃the preparation method of hollow nano-sphere, is characterized in that: in step (2), the quality mol ratio of the nano carbon microsphere adding and four hydration manganese acetates is 1:(0.5～2) g/mmol.

5. FeMnO according to claim 1 ₃the preparation method of hollow nano-sphere, is characterized in that:

(1) Iron(III) chloride hexahydrate of the four hydration manganese acetates of 0.5mmol and 0.5mmol is dissolved in the absolute ethyl alcohol of 10ml;

(2) 0.5g nano carbon microsphere is added in the mixed solution of step (1) to ultrasonic being uniformly dispersed;

(3) ethanolic solution that 5ml is contained to 0.5ml concentrated ammonia liquor dropwise joins in the suspension obtaining in step (2), stirs it is evenly mixed;

(4) under room temperature after standing 3h, centrifugation, water and absolute ethyl alcohol respectively wash three times, and the solid obtaining is dry at 60 ℃;

(5) sample after drying is put into Muffle furnace, from room temperature, with the heating rate of 1 ℃/min, rise to respectively 400 ℃, 500 ℃ and 650 ℃ keep 5h, naturally lower the temperature, and are cooled to room temperature, obtain FeMnO ₃hollow nano-sphere.

6. FeMnO described in claim 1 ₃the FeMnO that the preparation method of hollow nano-sphere prepares ₃hollow nano-sphere is as the application of electrode material for super capacitor.

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