CN112357954A - Shuttle structure H2Ti5O11·H2Solvothermal synthesis method of O nano material and application of lithium battery electrode material - Google Patents

Shuttle structure H2Ti5O11·H2Solvothermal synthesis method of O nano material and application of lithium battery electrode material Download PDF

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CN112357954A
CN112357954A CN202011271869.1A CN202011271869A CN112357954A CN 112357954 A CN112357954 A CN 112357954A CN 202011271869 A CN202011271869 A CN 202011271869A CN 112357954 A CN112357954 A CN 112357954A
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nano material
synthesis method
steps
shuttle
application
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CN112357954B (en
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李兆乾
莫立娥
胡林华
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Anhui Institute Of Industrial Technology Innovation
Hefei Institutes of Physical Science of CAS
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Anhui Institute Of Industrial Technology Innovation
Hefei Institutes of Physical Science of CAS
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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 shuttle-shaped structure H2Ti5O11·H2A solvothermal synthesis method of O nano material comprises the steps of adding ethylenediamine into methanol to be mixed to form a mixed solvent, adding tetra-n-butyl titanate, fully stirring, reacting in a reaction kettle at 160-230 ℃ for 6-24 hours, naturally cooling, separating, washing and drying to obtain a fusiform structure H2Ti5O11·H2And (4) O nano material. The synthesis method of the invention has a reaction stripMild reaction condition, simple method and uniform product appearance. Fusiform structure H synthesized by the method of the invention2Ti5O11·H2The O nano material has wide application prospect in the fields of novel solar cells, photocatalysis, lithium ion batteries and the like.

Description

Shuttle structure H2Ti5O11·H2Solvothermal synthesis method of O nano material and application of lithium battery electrode material
Technical Field
The invention belongs to the preparation of inorganic nano materials, and particularly relates to a fusiform structure H2Ti5O11·H2A solvent thermal synthesis method of O nano material and application of lithium battery electrode material.
Background
The shape and structure of the material are of great importance to the performance and application of the material. The specific morphology can be generally endowed with some specific properties of the material, such as that a one-dimensional nano array has excellent electron transmission performance, a core-shell micro-nano structure has excellent light scattering performance, a polyhedral micro-nano material can form a high-index surface to influence the catalytic reaction activity of the material, and a sea urchin-shaped structure has comprehensive properties of a multi-dimensional structure. Therefore, the synthesis of the micro-nano material with specific morphology has important significance.
Titanate has special structure and properties, has huge application prospect in the fields of electroluminescence, ion batteries, photocatalysis, solar energy conversion and the like, and is widely concerned by broad students. Titanate materials have various preparation methods, and can be classified into different types such as a solid phase method, a liquid phase method, an anodic oxidation method, an electrostatic spinning method and the like according to different process characteristics, wherein the solid phase method and the liquid phase method are most common. The solid phase method belongs to the traditional method, is usually used for large-scale production due to simple process and easily-controlled flow, and has the obvious defects of high reaction temperature, long time, high energy consumption, uncontrollable product morphology and the like. In comparison, the hydrothermal/solvothermal technology has the advantages of mild reaction conditions, simplicity and convenience in operation, low energy consumption and controllable product morphology, and is an ideal method for preparing the high-performance titanate micro-nano material.
The amino group on the organic amine compound has strong coordination capacity, so that the structure guiding effect can be played in the synthesis process of the micro-nano material to guide the product morphology structure, and the micro-nano material with a specific morphology structure is obtained. Methanol and ethylenediamine are conventional reagents, but methanol is usedAnd ethylenediamine as a mixed solvent to synthesize H2Ti5O11·H2O micro-nano materials have not been reported. In the invention, a simple one-step solvothermal method is adopted to synthesize the fusiform structure H with uniform appearance2Ti5O11·H2The O nano material has no template and post-treatment in the synthesis process, and the method is simple and easy.
Disclosure of Invention
The invention aims to provide a shuttle-shaped structure H2Ti5O11·H2A solvent thermal synthesis method of O nano material. The method has the advantages of simple operation, no template and no post-treatment, and can quickly synthesize the fusiform structure H under the condition of lower temperature2Ti5O11·H2And (4) O nano material.
The specific synthesis method comprises the following steps: adding ethylenediamine into the solvent to form a mixed solvent, uniformly stirring, adding tetra-n-butyl titanate, fully stirring, transferring the mixed solution into a reaction kettle, reacting at the temperature of 160 ℃ and 230 ℃ for 6-24 hours, naturally cooling, centrifuging, washing and drying to obtain the fusiform structure H2Ti5O11·H2And (4) O nano material.
The solvent is methanol, and the dosage of the ethylenediamine is 0.1-1 mL.
The size of the product spindle-shaped structure nano material is 800-1500 nm.
The size of the constituent nanobelt of the spindle-shaped structure nano material is 10-50 nm.
The invention also provides a fusiform structure H2Ti5O11·H2The O nano material is applied to the fields of solar batteries, lithium ion batteries and photocatalysis.
Compared with the prior synthesis technology, the invention adopts methanol as a conventional solvent, utilizes the coordination of amino groups in ethylenediamine molecules to regulate and control the shape and structure of the nano material, and prepares the fusiform structure H by a simple solvothermal method2Ti5O11·H2And (4) O nano material. In the synthesis process, no template and no post-treatment step are required, and the synthesis method has reactionMild condition, simple process, strong controllability and good reproducibility. Synthesized fusiform structure H of the invention2Ti5O11·H2The O nano material has wide application in the fields of solar batteries, lithium ion batteries, photocatalysis and the like.
Drawings
FIG. 1 is H of example 1 of the present invention2Ti5O11·H2SEM photograph of O
FIG. 2 is H of example 1 of the present invention2Ti5O11·H2TEM photograph of O.
FIG. 3 is H of example 1 of the present invention2Ti5O11·H2XRD spectrum of O.
Fig. 4 is a charge-discharge curve of the assembled battery of example 1 of the present invention.
Fig. 5 is a graph showing the cycle curve of the assembled battery of example 1 of the present invention.
Detailed Description
Example 1:
50mL of methanol and 0.1mL of ethylenediamine were mixed to form a mixed solvent, and after stirring uniformly, 2mL of tetra-n-butyl titanate (TBT) was added, and then the mixed solution was transferred to a reaction vessel with sufficient stirring and reacted at 200 ℃ for 24 hours. Naturally cooling, centrifuging, washing, and drying to obtain H2Ti5O11·H2The O-fusiform structured nanomaterial (FIG. 1).
Fig. 1-3 illustrate the structural and compositional characterization of the products prepared in this application.
Test example 1:
the application of the product in the lithium battery is as follows: with H of example 1 of the invention2Ti5O11·H2O is taken as a positive electrode material, and the mass ratio of the positive electrode material: carbon black conductive agent: uniformly mixing PVDF binder in a ratio of 7:2:1, coating the mixture on a 500-mesh stainless steel net, and drying to obtain a positive plate; assembling a 2032 type button battery in a glove box by using a metal lithium sheet as a negative electrode sheet, a glass fiber membrane (Celgard 2400) as a diaphragm and 1mol/L LiPF6 electrolyte, and sealing at 100mA/g currentAnd (5) carrying out electrochemical performance test at the temperature. The results of the charge/discharge and cycle curve tests of the battery are shown in fig. 4.
Fig. 4 is a charge and discharge curve of the battery, and fig. 5 is a cycle curve. As can be seen from fig. 4-5, at a current density of 100mA/g, the initial specific discharge capacity of the battery device is 158mAh/g, the second cycle rises to 285mAh/g, and then there is a certain degree of attenuation, but the specific discharge capacity of 170mAh/g can still be maintained after 50 cycles, and the coulomb efficiency approaches 100%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (5)

1. Fusiform structure H2Ti5O11·H2The solvothermal synthesis method of the O nano material is characterized by comprising the following steps of: adding ethylenediamine into the solvent to form a mixed solvent, uniformly stirring, adding tetra-n-butyl titanate, fully stirring, transferring the mixed solution into a reaction kettle, reacting at the temperature of 160 ℃ and 230 ℃ for 6-24 hours, naturally cooling, centrifuging, washing and drying to obtain the fusiform structure H2Ti5O11·H2And (4) O nano material.
2. Shuttle structure H according to claim 12Ti5O11·H2The solvothermal synthesis method of the O nano material is characterized by comprising the following steps: the solvent is methanol, and the dosage of the ethylenediamine is 0.1-1 mL.
3. Shuttle structure H according to claim 12Ti5O11·H2The solvothermal synthesis method of the O nano material is characterized by comprising the following steps: the size of the product spindle-shaped structure nano material is 800-1500 nm.
4. According to claimShuttle Structure H according to claim 12Ti5O11·H2The solvothermal synthesis method of the O nano material is characterized by comprising the following steps: the size of the constituent nanobelt of the spindle-shaped structure nano material is 10-50 nm.
5. Shuttle structure H according to claim 12Ti5O11·H2The O nano material is applied to the fields of lithium ion batteries and photocatalysis.
CN202011271869.1A 2020-11-13 2020-11-13 Shuttle structure H 2 Ti 5 O 11 ·H 2 Solvothermal synthesis method of O nano material and application of lithium battery electrode material Active CN112357954B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101327949A (en) * 2008-05-26 2008-12-24 武汉理工大学 Preparation of one-dimensional titanate radical nanopipe material and use thereof
CN101580276A (en) * 2009-06-19 2009-11-18 华南理工大学 Preparation method of highly dispersive spindle-shaped nano titanium dioxide sol
WO2011019322A1 (en) * 2009-08-11 2011-02-17 Nanyang Technological University Titanate / titania composite nanoparticle
CN102765708A (en) * 2012-07-09 2012-11-07 陕西科技大学 Microwave hydrothermal method for synthesizing lithium iron phosphate serving as cathode material of lithium ion battery
CN107686129A (en) * 2017-08-01 2018-02-13 中国科学院合肥物质科学研究院 A kind of TiO2The solvent process for thermosynthesizing of flower-shaped hierarchy sub-micron ball
CN109718859A (en) * 2019-01-08 2019-05-07 东北师范大学 A kind of Ag/TiO2/ MIL-125 (Ti) composite material and preparation method and Morphological control

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101327949A (en) * 2008-05-26 2008-12-24 武汉理工大学 Preparation of one-dimensional titanate radical nanopipe material and use thereof
CN101580276A (en) * 2009-06-19 2009-11-18 华南理工大学 Preparation method of highly dispersive spindle-shaped nano titanium dioxide sol
WO2011019322A1 (en) * 2009-08-11 2011-02-17 Nanyang Technological University Titanate / titania composite nanoparticle
CN102765708A (en) * 2012-07-09 2012-11-07 陕西科技大学 Microwave hydrothermal method for synthesizing lithium iron phosphate serving as cathode material of lithium ion battery
CN107686129A (en) * 2017-08-01 2018-02-13 中国科学院合肥物质科学研究院 A kind of TiO2The solvent process for thermosynthesizing of flower-shaped hierarchy sub-micron ball
CN109718859A (en) * 2019-01-08 2019-05-07 东北师范大学 A kind of Ag/TiO2/ MIL-125 (Ti) composite material and preparation method and Morphological control

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RUI ZHOU等: ""H2Ti5O11·H2O nanorod arrays formed on a Ti surface via a hybrid technique of microarc oxidation and chemical treatment"", 《CRYSTENGCOMM》 *

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