CN105967226A - Titanate nano-fiber and production method thereof - Google Patents

Titanate nano-fiber and production method thereof Download PDF

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Publication number
CN105967226A
CN105967226A CN201610286755.1A CN201610286755A CN105967226A CN 105967226 A CN105967226 A CN 105967226A CN 201610286755 A CN201610286755 A CN 201610286755A CN 105967226 A CN105967226 A CN 105967226A
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fiber
solution
titanate
electrostatic spinning
nano
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CN105967226B (en
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李星
朱聪聪
吴显宗
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Huzhou You Yan Intellectual Property Service Co.,Ltd.
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Ningbo University
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a preparation method of a titanate nano-fiber. The method comprises the following steps: dissolving certain amounts of lithium acetate, a barium salt and a titanium salt in a dimethyl formamide, acetate acid gracial and methanol mixed solution, adding polyvinylpyrrolidone used as a dispersant to form a clear solution, carrying out electrostatic spinning on the clear solution under a certain voltage at a certain volume flow rate, carrying out constant-temperature drying on the above obtained electrostatic spinning product, and carrying out high temperature sintering to obtain the corresponding BaTiO3.Li2TiO3 titanate nano-fiber. The electrochemical performances and the lithium storage performance of the nano-fiber are researched. The method successfully realizes production of the lithium ion battery negative electrode material BaTiO3.Li2TiO3 titanate nano-fiber, and the nano-fiber has excellent physical and chemical performances. Electrochemical experiments prove that the BaTiO3.Li2TiO3 titanate nano-fiber produced through the method has wide application prospect as a lithium ion battery negative electrode material. The production method has the advantages of simple operation, low raw material cost, less device investment, and suitableness for batch production in the whole production process.

Description

A kind of titanate nanofiber and preparation method thereof
Technical field
The invention belongs to lithium ion battery negative material field, be specifically related to a kind of titanate lithium ion battery negative material BaTiO3·Li2TiO3The preparation method of nanofiber.
Background technology
Lithium ion battery because its running voltage is high, specific energy is big, have extended cycle life, self-discharge rate is low, memory-less effect and right Advantages of environment protection, is not only widely used in the portable sets such as mobile phone, video camera, notebook computer, goes back quilt It is classified as candidate's power supply of Aero-Space, military affairs and energy storage.Negative material is as the important component part of lithium ion battery, to electricity The cost in pond and performance all play very important effect.
Metatitanic acid barium-lithium because of have have extended cycle life, the advantage such as stable in properties, safety so that it is be expected in terms of motive-power battery send out Wave important application.The performance of lithium ion battery of metatitanic acid barium-lithium is studied the most fewer by people at present.The solid phase method such as Lin Xiaoting Prepare granular BaLi2Ti6O14And test its circulation and high rate performance (Journal of Power Sources, 2015, 278,546-554), however result is the most preferable.People are again to BaLi subsequently2Ti6O14Being doped process, performance has one Fixed promote but expected value away from us also has the longest distance (Electrochimica Acta, 2015,186,24-33).Solid phase legal system Standby go out material generally have that granule is relatively big, form the shortcomings such as uneven, easy reunion, seriously govern the performance of material.
Famous Nobel laureate Feyneman once foretold in the sixties in 20th century: if our rule small to object Arrangement on mould is if in addition certain controls, and we just can make object obtain substantial amounts of thundering characteristic, just can be appreciated that material The performance of material produces abundant change.His described material is exactly present nano material.It is reduced in size to nanometer when particle Magnitude, it will cause sound, optical, electrical, magnetic, hot property to present new characteristic.In all of nano material, 1-dimention nano Material makes it have the performance of excellence at the numerous areas such as optical, electrical, magnetic, catalysis, sensor and dive because of its structure and 1D form Application prospect.Meanwhile, monodimension nanometer material is also the basis of other low-dimension nano materials research.Therefore, 1-dimention nano material Material has become as forward position and the study hotspot in current nanometer material science field.
In order to solve the various shortcomings of lithium titanate battery material prepared by solid phase method, promote the electricity of lithium titanate battery material further Chemical property, the present invention uses electrostatic spinning technique to be prepared for a kind of metatitanic acid barium-lithium BaTiO3·Li2TiO3Nanofiber.
Summary of the invention
The present invention's is the problem in order to solve the chemical property of the lithium titanate cell negative pole material that solid phase method is prepared difference, it is provided that A kind of titanate cell negative electrode material BaTiO3·Li2TiO3The preparation method of nanofiber.
The present invention solves that the technical scheme that above-mentioned technical problem is used is: a kind of titanate nanofiber, this titanation Formula is BaTiO3·Li2TiO3。
Present invention also offers the preparation method of a kind of titanate nanofiber, described preparation method includes:
(1) by LiCH3COO and barium salt are dissolved in the mixed solvent of dimethylformamide (DMF) and methanol (MeOH) (DMF and MeOH volume ratio is 1:1), stirs 0.5h, forms solution A；
(2) titanium salt is dissolved in solution A, adds glacial acetic acid, stir 0.5h, form solution B；
(3) polyvinylpyrrolidone (PVP) is added solution B, stir 2h, form the solution C of clarification, solution C Middle Li, Ba are 2.2:1:3 with the mol ratio of Ti element；
(4) by clarification solution C 13～17.5kV voltage and 0.6mL h-1Flow rate under electrostatic spinning；
(5) the electrostatic spinning product obtained is put at 100 DEG C dry 6～12h；
(6) dried electrostatic spinning product is transferred in Muffle furnace, at 750～900 DEG C, sinter 5h, obtain metatitanic acid Salt nanofiber.
Alternatively, described barium salt is Ba (CH3COO)2、BaCl2In one or both compositions.
Alternatively, described titanium salt is butyl titanate.
Compared with prior art, advantages of the present invention and innovative point are as follows:
The titanate BaTiO of present invention synthesis3·Li2TiO3Nanofiber is as cell negative electrode material excellent performance, charge and discharge electrical measurement Take temperature bright, the BaTiO of preparation3·Li2TiO3Titanate nanofiber is at 1000mA g-1Electric current density under charge and discharge cycles 800 Week, specific capacity was without substantially decay.The BaLi prepared with conventional solid-state method2Ti6O14Granule is compared, BaTiO3·Li2TiO3Nanometer The chemical property of fiber has had and has significantly promoted.This also carries for the new commercially viable lithium ion battery negative material of searching Supply thinking.
Accompanying drawing explanation
Fig. 1 is the BaTiO that embodiment prepares3·Li2TiO3The XRD figure of titanate nanofiber；
Fig. 2 is the BaTiO that embodiment prepares3·Li2TiO3The SEM figure of titanate nanofiber.
Detailed description of the invention
Technical solution of the present invention is not limited to act detailed description of the invention set forth below, and also include between each detailed description of the invention is any Combination.
Embodiment 1
By 2.2mmol LiCH3COO and 1.0mmol Ba (CH3COO)2Be dissolved in 20mL dimethylformamide (DMF) and Stirring 0.5h in the mixed solvent (volume ratio is 1:1) of methanol, forms solution A；3.0mmol butyl titanate is dissolved in molten Liquid A, adds 6mL glacial acetic acid, stirs 0.5h, forms solution B；Polyvinylpyrrolidone 2.0g is added solution B, stirs Mix 2h, form solution C；By the solution C of clarification at the voltage of 13kV and 0.6mL h-1Flow rate under carry out electrostatic spinning； The electrostatic spinning product obtained is put at 100 DEG C and is dried 6h；Dried electrostatic spinning product is transferred in Muffle furnace, Sinter 5h at 750 DEG C, obtain lithium ion battery negative material BaTiO3·Li2TiO3Titanate nanofiber.Use powder diffraction (XRD) described nanofiber is characterized, as shown in Figure 1.With the pattern of nanofiber described in scanning electron microscopic observation, As shown in Figure 2.
Embodiment 2
By 2.2mmol LiCH3COO and 1.0mmol BaCl2It is dissolved in the mixed of 20mL dimethylformamide (DMF) and methanol Stirring 0.5h in bonding solvent (volume ratio is 1:1), forms solution A；3.0mmol butyl titanate is dissolved in solution A, adds 6mL glacial acetic acid, stirs 0.5h, forms solution B；2.0g polyvinylpyrrolidone is added solution B, stirs 2h, shape Become solution C；By the solution C of clarification at the voltage of 17.5kV and 0.6mL h-1Flow rate under carry out electrostatic spinning；To obtain Electrostatic spinning product be put at 100 DEG C be dried 9h；Dried electrostatic spinning product is transferred in Muffle furnace, at 850 DEG C Sintering 5h, obtains lithium ion battery negative material BaTiO3·Li2TiO3Titanate nanofiber.
Embodiment 3
By 2.2mmol LiCH3COO and 1.0mmol Ba (CH3COO)2Be dissolved in 20mL dimethylformamide (DMF) and Stirring 0.5h in the mixed solvent (volume ratio is 1:1) of methanol, forms solution A；3.0mmol butyl titanate is dissolved in molten Liquid A, adds 6mL glacial acetic acid, stirs 0.5h, forms solution B；2.0g polyvinylpyrrolidone is added solution B, stirs Mix 2h, form solution C；By the solution C of clarification at the voltage of 15kV and 0.6mL h-1Flow rate under carry out electrostatic spinning； The electrostatic spinning product obtained is put at 100 DEG C and is dried 12h；Dried electrostatic spinning product is transferred in Muffle furnace, Sinter 5h at 900 DEG C, obtain lithium ion battery negative material BaTiO3·Li2TiO3Titanate nanofiber.

Claims (3)

1. a titanate nanofiber, it is characterised in that this titanate chemical formula is BaTiO3·Li2TiO3。
2. the preparation method of the titanate nanofiber described in a claim 1, it is characterised in that described preparation method includes:
(1) by LiCH3COO and barium salt are dissolved in mixed solvent (DMF and the methanol of dimethylformamide (DMF) and methanol Volume ratio is 1:1) middle stirring 0.5h, form solution A；
(2) titanium salt is dissolved in solution A, adds glacial acetic acid, stir 0.5h, form solution B；
(3) polyvinylpyrrolidone (PVP) is added solution B, stir 2h, form the solution C of clarification, solution C Middle Li, Ba are 2.2:1:3 with the mol ratio of Ti element；
(4) by clarification solution C 13～17.5kV voltage and 0.6mL h-1Flow rate under electrostatic spinning；
(5) the electrostatic spinning product obtained is put at 100 DEG C dry 6～12h；
(6) dried electrostatic spinning product is transferred in Muffle furnace, at 750～900 DEG C, sinter 5h, obtain metatitanic acid Salt nanofiber.
The preparation method of titanate nanofiber the most according to claim 2, it is characterised in that described barium salt is Ba(CH3COO)2、BaCl2In one or both compositions, described titanium salt is butyl titanate.
CN201610286755.1A 2016-04-29 2016-04-29 A kind of titanate nanofiber and preparation method thereof Active CN105967226B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108649200A (en) * 2018-05-08 2018-10-12 宁波大学 A kind of LaTi21O38·CoTiO3·Mn3O4The preparation method of compound nano wire
CN110079895A (en) * 2019-05-21 2019-08-02 宁波大学 A kind of titanate and titanium dioxide compound nano wire and preparation method thereof
CN111607846A (en) * 2020-06-09 2020-09-01 宁波大学 Preparation method and application of titanate lithium ion battery negative electrode material
CN112275306A (en) * 2020-11-20 2021-01-29 华北理工大学 Simple calcination method for preparing BaTiO3/g-C3N4Method for preparing composite photocatalyst

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104201364A (en) * 2014-09-15 2014-12-10 李建明 Method for preparing spinel lithium titanate

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104201364A (en) * 2014-09-15 2014-12-10 李建明 Method for preparing spinel lithium titanate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CONGXUE SU ET AL.: ""Microwave Dielectric Properties of MLi2Ti6O14 [M=Ba and Sr] Ceramics and Their Compatibility with Sliver"", 《J. AM. CERAM. SOC.》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108649200A (en) * 2018-05-08 2018-10-12 宁波大学 A kind of LaTi21O38·CoTiO3·Mn3O4The preparation method of compound nano wire
CN110079895A (en) * 2019-05-21 2019-08-02 宁波大学 A kind of titanate and titanium dioxide compound nano wire and preparation method thereof
CN110079895B (en) * 2019-05-21 2021-09-17 宁波大学 Titanate and titanium dioxide composite nanowire and preparation method thereof
CN111607846A (en) * 2020-06-09 2020-09-01 宁波大学 Preparation method and application of titanate lithium ion battery negative electrode material
CN112275306A (en) * 2020-11-20 2021-01-29 华北理工大学 Simple calcination method for preparing BaTiO3/g-C3N4Method for preparing composite photocatalyst

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