CN104402044B - A kind of preparation method of barium titanate/graphene composite nano material - Google Patents

A kind of preparation method of barium titanate/graphene composite nano material Download PDF

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CN104402044B
CN104402044B CN201410644234.XA CN201410644234A CN104402044B CN 104402044 B CN104402044 B CN 104402044B CN 201410644234 A CN201410644234 A CN 201410644234A CN 104402044 B CN104402044 B CN 104402044B
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barium titanate
composite nano
nano material
graphene composite
preparation
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CN104402044A (en
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韩高荣
姜姗
任召辉
赵若愚
魏晓
沈鸽
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/006—Alkaline earth titanates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • 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
    • 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
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The present invention relates to a kind of preparation method of barium titanate/graphene composite nano material, what the method adopted is wet-chemical reaction method.Its preparation process comprises: using ethylene glycol monomethyl ether as the solvent dissolving titanium ion, utilize ammoniacal liquor as precipitation agent precipitated titanium ion, add graphene oxide water solution and fully mix; Utilize the deionized water solution of barium acetate as barium source, quadrol and thanomin mixing solutions are as solvent; Finally utilize mineralizer potassium hydroxide to promote crystallization, obtain barium titanate/graphene nano powder through hydro-thermal reaction.Present invention process process is simple, is easy to control, and pollution-free, cost is low; Obtained barium titanate/graphene composite nano material, purity is high, good crystallinity.

Description

A kind of preparation method of barium titanate/graphene composite nano material
Technical field
The present invention relates to the preparation method of barium titanate/graphene composite nano material, belong to field of inorganic nonmetallic material.
Background technology
Barium titanate is a kind of ferroelectric material of typical perovskite structure, has a wide range of applications space in fields such as thermistor, nonlinear circuit component, dielectric amplifier, laminated ceramic capacitor (MLCC) and Nonvolatile ferroelectric memories.Graphene is that one passes through sp by carbon atom 2hydridization composition, have the Two-dimensional Carbon material of an atomic thickness, its intensity is 100 times of ferrous materials, has superpower electroconductibility simultaneously, is a kind of desirable super capacitor material.At present, for the research of the Hybrid capacitor material of barium titanate and Graphene, be still in the exploratory stage, be showed no relevant report both at home and abroad.
Summary of the invention
The object of the present invention is to provide a kind of technique simple, process is easy to the preparation method of the barium titanate/graphene composite nano material controlled.
The preparation method of barium titanate/graphene composite nano material of the present invention, employing be wet-chemical reaction method, comprise following processing step:
1) 0.25-0.5mmol tetrabutyl titanate is dissolved in 5ml ethylene glycol monomethyl ether, instillation mass concentration 30% ammoniacal liquor, as precipitation agent precipitated titanium ion, obtains the oxyhydroxide precipitation of titanium;
2) the oxyhydroxide precipitation of titanium step 1) obtained, 10ml concentration is that 0.5-2g/L graphene oxide water solution and 20ml quadrol/thanomin mixed solution join in reactor inner bag together, wherein, the volume ratio of quadrol and thanomin is 1:1, and stirred at ambient temperature is 6h at least;
3) 0.25-0.5mmol barium acetate is dissolved in 2ml deionized water, joins step 2) be equipped with in the reactor inner bag of mixing solutions, add 2.74 ~ 10.96g potassium hydroxide subsequently, stirred at ambient temperature is 30min at least;
4) the reactor inner bag being configured with reaction mass is placed in reactor, airtight, at 180-200 oc insulation is after 8-12 hour, and Temperature fall, to room temperature, takes out reaction product, filters, and by washed with de-ionized water, dries, obtains barium titanate/Graphene composite nano powder.
In the present invention, described barium acetate, butyl (tetra) titanate, ethylene glycol monomethyl ether, potassium hydroxide, quadrol, thanomin and graphene oxide purity are all not less than chemical pure.
In the present invention, described reactor is polytetrafluoroethylliner liner, the reactor that stainless steel external member is airtight.
Present invention process process is simple, is easy to control, and pollution-free, cost is low; Obtained barium titanate/graphene composite nano material, purity is high, good crystallinity.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of barium titanate/graphene composite nano material.
Fig. 2 is the XRD figure spectrum of barium titanate/graphene composite nano material.
Fig. 3 is the transmission electron microscope picture of barium titanate/graphene composite nano material.
Embodiment
Below in conjunction with embodiment, the inventive method is described in further detail.
Embodiment 1
1) 0.25mmol tetrabutyl titanate is dissolved in 5ml ethylene glycol monomethyl ether, instillation mass concentration 30% ammoniacal liquor, as precipitation agent precipitated titanium ion, obtains the oxyhydroxide precipitation of titanium;
2) the oxyhydroxide precipitation of titanium step 1) obtained, 10ml concentration is that 0.5g/L graphene oxide water solution and 20ml quadrol/thanomin mixed solution join in reactor inner bag together, wherein, the volume ratio of quadrol and thanomin is 1:1, stirred at ambient temperature 6h;
3) 0.25mmol barium acetate is dissolved in 2ml deionized water, joins step 2) be equipped with in the reactor inner bag of mixing solutions, add 2.74g potassium hydroxide subsequently, stirred at ambient temperature 30min;
4) the reactor inner bag being configured with reaction mass is placed in reactor, airtight, 180 oafter C is incubated 12 hours, Temperature fall, to room temperature, takes out reaction product, filters, and by washed with de-ionized water, dries, obtains barium titanate/Graphene composite nano powder.Its scanning electron microscopic picture as shown in Figure 1.
Embodiment 2
1) 0.3mmol tetrabutyl titanate is dissolved in 5ml ethylene glycol monomethyl ether, instillation mass concentration 30% ammoniacal liquor, as precipitation agent precipitated titanium ion, obtains the oxyhydroxide precipitation of titanium;
2) the oxyhydroxide precipitation of titanium step 1) obtained, 10ml concentration is that 1g/L graphene oxide water solution and 20ml quadrol/thanomin mixed solution join in reactor inner bag together, wherein, the volume ratio of quadrol and thanomin is 1:1, stirred at ambient temperature 8h;
3) 0.3mmol barium acetate is dissolved in 2ml deionized water, joins step 2) be equipped with in the reactor inner bag of mixing solutions, add 5.48g potassium hydroxide subsequently, stirred at ambient temperature 60min;
4) the reactor inner bag being configured with reaction mass is placed in reactor, airtight, 190 oafter C is incubated 12 hours, Temperature fall, to room temperature, takes out reaction product, filters, and by washed with de-ionized water, dries, obtains barium titanate/Graphene composite nano powder.
The transmission electron microscope picture of its correspondence and XRD spectral line are as Fig. 2, and shown in 3, gained sample crystallization degree is good, and purity is high, and the barium titanate nano particle size distribution on Graphene is little, good dispersity.
Embodiment 3
1) 0.5mmol tetrabutyl titanate is dissolved in 5ml ethylene glycol monomethyl ether, instillation mass concentration 30% ammoniacal liquor, as precipitation agent precipitated titanium ion, obtains the oxyhydroxide precipitation of titanium;
2) the oxyhydroxide precipitation of titanium step 1) obtained, 10ml concentration is that 2g/L graphene oxide water solution and 20ml quadrol/thanomin mixed solution join in reactor inner bag together, wherein, the volume ratio of quadrol and thanomin is 1:1, stirred at ambient temperature 10h;
3) 0.5mmol barium acetate is dissolved in 2ml deionized water, joins step 2) be equipped with in the reactor inner bag of mixing solutions, add 10.96g potassium hydroxide subsequently, stirred at ambient temperature 60min;
4) the reactor inner bag being configured with reaction mass is placed in reactor, airtight, 200 oafter C is incubated 12 hours, Temperature fall, to room temperature, takes out reaction product, filters, and by washed with de-ionized water, dries, obtains barium titanate/Graphene composite nano powder.

Claims (3)

1. a preparation method for barium titanate/graphene composite nano material, is characterized in that comprising following processing step:
1) 0.25-0.5mmol tetrabutyl titanate is dissolved in 5mL ethylene glycol monomethyl ether, instillation mass concentration 30% ammoniacal liquor, as precipitation agent precipitated titanium ion, obtains the oxyhydroxide precipitation of titanium;
2) the oxyhydroxide precipitation of titanium step 1) obtained, 10mL concentration is that 0.5-2g/L graphene oxide water solution and 20mL quadrol/thanomin mixed solution join in reactor inner bag together, wherein, the volume ratio of quadrol and thanomin is 1:1, and stirred at ambient temperature is 6h at least;
3) 0.25-0.5mmol barium acetate is dissolved in 2mL deionized water, joins step 2) be equipped with in the reactor inner bag of mixing solutions, add 2.74 ~ 10.96g potassium hydroxide subsequently, stirred at ambient temperature is 30min at least;
4) the reactor inner bag being configured with reaction mass is placed in reactor, airtight, at 180-200 oafter C is incubated 12 hours, Temperature fall, to room temperature, takes out reaction product, filters, and by washed with de-ionized water, dries, obtains barium titanate/graphene composite nano material.
2. the preparation method of barium titanate/graphene composite nano material according to claim 1, is characterized in that described barium acetate, butyl (tetra) titanate, ethylene glycol monomethyl ether, potassium hydroxide, quadrol, thanomin and graphene oxide purity are all not less than chemical pure.
3. the preparation method of barium titanate/graphene composite nano material according to claim 1, is characterized in that described reactor is polytetrafluoroethylliner liner, the reactor that stainless steel external member is airtight.
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CN104962232A (en) * 2015-06-24 2015-10-07 南京理工大学 Fe3O4@BaTiO3/RGO ternary composite wave-absorbing material and preparation method thereof
CN105126803A (en) * 2015-08-25 2015-12-09 浙江大学 Preparation method of strontium titanate/graphene composite nanometer catalyst
CN107935056B (en) * 2017-12-01 2019-07-09 陕西科技大学 A kind of preparation method of porous cobalt titanate micron bar with six prismatics and rGO composite air-sensitive material
CN108219369B (en) * 2017-12-07 2020-04-28 华南理工大学 Composite filling powder, polymer-based composite dielectric material, and preparation and application thereof
CN109942997A (en) * 2019-04-03 2019-06-28 大连大学 A kind of graphene oxide-barium titanate dielectric composite film and preparation method thereof
CN109942893A (en) * 2019-04-03 2019-06-28 大连大学 A kind of barium titanate-graphene oxide composite nano-grade sheet and preparation method thereof
CN112480717B (en) * 2019-09-11 2022-05-03 哈尔滨工业大学 Method for preparing core-shell structure nano composite particles by aerogel method

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CN102437321A (en) * 2011-12-20 2012-05-02 中国科学院新疆理化技术研究所 Graphene-TiO2(B) nanotube composite material and preparation method thereof
CN102887705A (en) * 2012-10-24 2013-01-23 浙江大学 Preparation method of tetragonal-phase barium titanate (BaTiO3) hollow nanocrystal

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WO2012115931A1 (en) * 2011-02-22 2012-08-30 Purdue Research Foundation Synthesis of metal oxide-based thermoelectric materials for high temperature applications

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Publication number Priority date Publication date Assignee Title
CN102437321A (en) * 2011-12-20 2012-05-02 中国科学院新疆理化技术研究所 Graphene-TiO2(B) nanotube composite material and preparation method thereof
CN102887705A (en) * 2012-10-24 2013-01-23 浙江大学 Preparation method of tetragonal-phase barium titanate (BaTiO3) hollow nanocrystal

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