CN104402044A - Preparation method for barium titanate/graphene composite nanometer material - Google Patents

Preparation method for barium titanate/graphene composite nanometer material Download PDF

Info

Publication number
CN104402044A
CN104402044A CN201410644234.XA CN201410644234A CN104402044A CN 104402044 A CN104402044 A CN 104402044A CN 201410644234 A CN201410644234 A CN 201410644234A CN 104402044 A CN104402044 A CN 104402044A
Authority
CN
China
Prior art keywords
barium titanate
graphene composite
preparation
reactor
barium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410644234.XA
Other languages
Chinese (zh)
Other versions
CN104402044B (en
Inventor
韩高荣
姜姗
任召辉
徐刚
肖珍
魏晓
刘双宇
王欣
屠芳芳
曾诗琪
沈鸽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN201410644234.XA priority Critical patent/CN104402044B/en
Publication of CN104402044A publication Critical patent/CN104402044A/en
Application granted granted Critical
Publication of CN104402044B publication Critical patent/CN104402044B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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 invention relates to a preparation method for a barium titanate/graphene composite nanometer material, and the method employs a wet chemical reaction process. The preparation steps comprise: taking 2-methoxyethanol as a solvent dissolving a titanium ion, utilizing ammonia water as a precipitating agent to precipitate titanium ion, adding an aqueous solution of graphene oxide, and fully mixing; utilizing a deionized water solution of barium acetate as a barium source, and taking a mixed solution of ethylenediamine and ethanolamine as a solvent; and finally utilizing a mineralization agent potassium hydroxide to promote crystallization, and performing hydro-thermal reaction to obtain the barium titanate/graphene nanometer powder. The preparation method is simple in process, easy to control, free of pollution and low in cost, and the prepared barium titanate/graphene composite nanometer material is high in purity and good in 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 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.
2. the preparation method of the barium titanate/graphene composite nano material according to claims 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 the barium titanate/graphene composite nano material according to claims 1, is characterized in that described reactor is polytetrafluoroethylliner liner, the reactor that stainless steel external member is airtight.
CN201410644234.XA 2014-11-14 2014-11-14 A kind of preparation method of barium titanate/graphene composite nano material Active CN104402044B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410644234.XA CN104402044B (en) 2014-11-14 2014-11-14 A kind of preparation method of barium titanate/graphene composite nano material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410644234.XA CN104402044B (en) 2014-11-14 2014-11-14 A kind of preparation method of barium titanate/graphene composite nano material

Publications (2)

Publication Number Publication Date
CN104402044A true CN104402044A (en) 2015-03-11
CN104402044B CN104402044B (en) 2016-01-20

Family

ID=52639731

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410644234.XA Active CN104402044B (en) 2014-11-14 2014-11-14 A kind of preparation method of barium titanate/graphene composite nano material

Country Status (1)

Country Link
CN (1) CN104402044B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN107935056A (en) * 2017-12-01 2018-04-20 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 materials
CN108219369A (en) * 2017-12-07 2018-06-29 华南理工大学 A kind of composite filled powder, polymer matrix composite dielectric materials and its preparation and application
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
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
CN112480717A (en) * 2019-09-11 2021-03-12 哈尔滨工业大学 Method for preparing core-shell structure nano composite particles by aerogel method

Citations (3)

* Cited by examiner, † Cited by third party
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
WO2012115931A1 (en) * 2011-02-22 2012-08-30 Purdue Research Foundation Synthesis of metal oxide-based thermoelectric materials for high temperature applications
CN102887705A (en) * 2012-10-24 2013-01-23 浙江大学 Preparation method of tetragonal-phase barium titanate (BaTiO3) hollow nanocrystal

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012115931A1 (en) * 2011-02-22 2012-08-30 Purdue Research Foundation Synthesis of metal oxide-based thermoelectric materials for high temperature applications
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

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN107935056A (en) * 2017-12-01 2018-04-20 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 materials
CN108219369A (en) * 2017-12-07 2018-06-29 华南理工大学 A kind of composite filled powder, polymer matrix composite dielectric materials and its preparation and application
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
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
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
CN112480717A (en) * 2019-09-11 2021-03-12 哈尔滨工业大学 Method for preparing core-shell structure nano composite particles by aerogel method
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

Also Published As

Publication number Publication date
CN104402044B (en) 2016-01-20

Similar Documents

Publication Publication Date Title
CN104402044B (en) A kind of preparation method of barium titanate/graphene composite nano material
Liu et al. Controllable synthesis of ultrathin layered transition metal hydroxide/zeolitic imidazolate framework-67 hybrid nanosheets for high-performance supercapacitors
CN103219168B (en) A kind of Li 4ti 5o 12/ graphene combination electrode material and preparation method thereof
CN104124467A (en) Method for preparing solid electrolyte by using lithium lanthanum zirconium oxide precursor coated powder
CN109616333B (en) Nitrogen-doped carbon nanotube/cobaltosic oxide composite material and preparation method thereof
CN102925979B (en) Method for preparing perovskite lead titanate crystal nanosheet
CN102139914B (en) Method for preparing calcium titanate nanoparticles
CN105126803A (en) Preparation method of strontium titanate/graphene composite nanometer catalyst
CN101311376A (en) Method for preparing strontium titanate nanometer powder of one-dimensional structure
CN111792672B (en) Branch cross-linked coralline micron-structured lithium-containing oxide powder material and preparation method thereof
CN106784693B (en) Preparation method of nitrogen-rich nano lithium titanate electrode material with uniform carbon coating layer on surface
CN105406042A (en) Preparation method for carbon-coated super-long titanium dioxide nanotube negative electrode material of lithium ion battery
Zhang et al. Facile synthesis and characterization of rough surface V _ 2 O _ 5 V 2 O 5 nanomaterials for pseudo-supercapacitor electrode material with high capacitance
Zhang et al. Multicomponent hybridization transition metal oxide electrode enriched with oxygen vacancy for ultralong‐life supercapacitor
Sari et al. Facile preparation of carbon nanofiber from banana peel waste
CN105070902A (en) Mixed transition metal based preparation method for cathode material of sodium secondary battery
CN103094549A (en) Supercritical hydro-thermal synthesizing method of lithium ion battery negative material lithium titanate
CN105449187A (en) Preparation method of high-performance co-doped lithium titanate electrode material
CN102139915A (en) Method for preparing calcium titanate nanospheres
CN110660986B (en) Tin-based composite material, preparation method and application thereof
Huang et al. Rapid amorphization in MOF/metal selenite nanocomposites for enhanced capacity in supercapacitors
CN102139913B (en) Method for preparing lead titanate nanoparticles
Chiu et al. A novel green approach to synthesis of nanostructured Li4Ti5O12 anode material
CN102139916A (en) Method for preparing strontium titanate nanoparticles
CN110577242A (en) Regular-hexagon nano-sheet tungsten disulfide electrode material and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C53 Correction of patent of invention or patent application
CB03 Change of inventor or designer information

Inventor after: Han Gaorong

Inventor after: Jiang Pan

Inventor after: Ren Zhaohui

Inventor after: Zhao Ruoyu

Inventor after: Wei Xiao

Inventor after: Shen Ge

Inventor before: Han Gaorong

Inventor before: Zeng Shiqi

Inventor before: Shen Ge

Inventor before: Jiang Pan

Inventor before: Ren Zhaohui

Inventor before: Xu Gang

Inventor before: Xiao Zhen

Inventor before: Wei Xiao

Inventor before: Liu Shuangyu

Inventor before: Wang Xin

Inventor before: Tu Fangfang

COR Change of bibliographic data

Free format text: CORRECT: INVENTOR; FROM: HAN GAORONG JIANG SHAN REN ZHAOHUI XU GANG XIAO ZHEN WEI XIAO LIU SHUANGYUWANG XIN TU FANGFANG CENG SHIQI SHEN GE TO: HAN GAORONG JIANG SHAN REN ZHAOHUI ZHAO RUOYU WEI XIAO SHEN GE

C14 Grant of patent or utility model
GR01 Patent grant