CN105948108A - Sodium lithium titanate nanowire and preparation method thereof - Google Patents

Sodium lithium titanate nanowire and preparation method thereof Download PDF

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CN105948108A
CN105948108A CN201610281086.9A CN201610281086A CN105948108A CN 105948108 A CN105948108 A CN 105948108A CN 201610281086 A CN201610281086 A CN 201610281086A CN 105948108 A CN105948108 A CN 105948108A
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sodium
lithium titanate
solution
lithium
electrostatic spinning
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CN105948108B (en
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李星
吴显宗
朱聪聪
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Binzhou Kechuang Incubator 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
    • C01G23/005—Alkali 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
    • 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
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • 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
    • 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

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Abstract

The invention discloses a preparation method for preparing a sodium lithium titanate nanowire. According to the invention, a certain amount of lithium salt, sodium salt and titanium salt is dissolved in a mixed solution of dimethylformamide and ethanol. Meanwhile, glacial acetic acid and a polymer are added to form a clear solution. The clear solution is subjected to electrostatic spinning under a certain voltage and at a certain volumetric flow rate. The product of the electrostatic spinning is dried at a constant temperature, and then is sintered at a high temperature to obtain the corresponding NaLiTiO3 sodium lithium titanate nanowire. According to the technical scheme of the invention, the electrochemical performance and the lithium storage performance of the sodium lithium titanate nanowire are studied. Meanwhile, the NaLiTiO3 sodium lithium titanate nanowire as lithium ion battery cathode materials is successively prepared. The nanowire is excellent in physical and chemical properties. Electrochemical experiments prove that, the prepared NaLiTiO3 sodium lithium titanate nanowire as lithium ion battery cathode materials is wide in application prospect. The entire preparation process is simple in operation, low in raw material cost, small in equipment investment, and suitable for batch production.

Description

A kind of sodium lithium titanate nano wire and preparation method thereof
Technical field
The invention belongs to field of lithium ion battery material, be specifically related to a kind of lithium ion battery negative material NaLiTiO3Metatitanic acid The preparation method of lithium sodium nanofiber.
Background technology
Sodium lithium titanate compound, as a kind of potential lithium ion battery material, has preferable ionic conductivity, higher reason Will not form the advantages such as solid electrolyte interface (SEI) film during opinion capacity, discharge and recharge, therefore this material is assembled into positive electrode Battery can obtain high output voltage, safely, the lithium ion battery that has extended cycle life, and be expected to meet electric powered motor need Ask.But the big high rate performance of sodium lithium titanate negative material is poor.
The method of the big high rate performance solving sodium lithium titanate negative material has a lot, and the most effective method is by material nano Change.The specific surface area of zero dimensional nanometer materials is big so that its electro-chemical activity surface can increase, and can cause the cycle performance of material Being deteriorated, compared to zero dimension, two and three dimensions nano material, monodimension nanometer material has superior physically and electrically performance, this For dimension and dimensional effect the research of the impact in terms of electric transmission, conduction of heat and engineering properties provided one good System.Monodimension nanometer material has important value in basic research field, also has in terms of integrated circuit nanometer components and parts Wide application prospect, research worker the most advantageously can be applied and integrated in them in nano functional electronic device.
At present, the sodium lithium titanate preparation method reported mainly has: high temperature solid phase synthesis and sol-gel process.High temperature solid-state There is the deficiencies such as sintering time length, temperature is high, energy consumption is big in method, and the material synthesized is more uneven, purity is relatively low, particle diameter The shortcomings such as bigger and chemical property relative mistake；And the preparation process of sol-gel process is more complicated, need to control reaction Temperature and the speed of solution dropping, and it also requires longer digestion time, increase cost.In order to solve above-mentioned two The shortcoming of kind of method also improves the big high rate performance of sodium lithium titanate material, and present invention method of electrostatic spinning prepares one-dimensional lithium titanate Sodium NaLiTiO3Nano-material.
Summary of the invention
The problem that the invention aims to solve the chemical property difference of existing sodium lithium titanate cell negative pole material, it is provided that one Plant lithium ionic cell cathode material lithium titanate sodium NaLiTiO3The preparation method of nano wire.
The present invention solves that the technical scheme that above-mentioned technical problem is used is: a kind of sodium lithium titanate nano wire, this sodium lithium titanate Chemical formula is NaLiTiO3。
Present invention also offers the preparation method of a kind of sodium lithium titanate nano wire, described preparation method includes:
Sodium salt is dissolved in dimethylformamide (DMF), forms solution A；
Lithium salts is dissolved in dehydrated alcohol, forms solution B；
Titanium salt is dissolved in dimethylformamide (DMF), forms solution C；
After solution A, B, C mixing, add glacial acetic acid and macromolecule, stir 2h, form the solution D of clarification, solution D Middle Na, Li are 1:1:3～1:1.5:3.5 with the mol ratio of Ti element；
The solution D of clarification is carried out electrostatic spinning under 15～20kV voltages and 0.8～1.2mL/h flow rate；
The electrostatic spinning product obtained is put in 60～90 DEG C of oven drying 4h；
Dried electrostatic spinning product is transferred in Muffle furnace, sinters 3～6h at 600～800 DEG C, obtain sodium lithium titanate Nano wire.
Preferably, described sodium salt is NaCH3COO、NaHCO3In one or both compositions, described lithium salts be LiF, LiCH3COO and LiNO3In a kind of or the most several compositionss, described titanium salt is isopropyl titanate, described macromolecule For polyvinyl alcohol (PVA).
One-dimensional sodium lithium titanate NaLiTiO of present invention synthesis3Nano-material excellent performance, has the higher specific volume that discharges first Amount and preferable capability retention, first discharge specific capacity is 80mAh g-1, after 800 cycle charge-discharges, capability retention It is not less than 90%.
Accompanying drawing explanation
Fig. 1 is sodium lithium titanate NaLiTiO that the present invention prepares3The XRD figure of nano wire；
Fig. 2 is sodium lithium titanate NaLiTiO that the present invention prepares3The SEM figure of nano wire.
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 the NaCH of 0.15mmol3COO is dissolved in 2mL dimethylformamide (DMF), forms solution A；By 0.15mmol LiCH3COO is dissolved in 5mL dehydrated alcohol, forms solution B；0.3mmol isopropyl titanate is dissolved in 3mL dimethyl methyl Amide (DMF), forms solution C；2mL glacial acetic acid and the poly-second of 1.2g will be added after solution A, B, C mix homogeneously Enol, stirs 2h, forms the solution D of clarification；The solution D of clarification is carried out under voltage 15kv and flow rate 0.8mL/h Electrostatic spinning；The electrostatic spinning product obtained is put in 60 DEG C of oven drying 4h；By dried electrostatic spinning product transfer In Muffle furnace, sinter 6h at 600 DEG C, obtain lithium ionic cell cathode material lithium titanate sodium NaLiTiO3Nano wire.With Described nano wire is characterized, as shown in Figure 1 by powder diffraction (XRD).With nano wire described in scanning electron microscopic observation Pattern, as shown in Figure 2.
Embodiment 2
By the NaHCO of 0.15mmol3It is dissolved in 2mL dimethylformamide (DMF), forms solution A；By 0.225mmol LiF be dissolved in 5mL dehydrated alcohol, form solution B；The isopropyl titanate of 0.525mmol is dissolved in 3mL dimethyl methyl Amide (DMF), forms solution C；1.5mL glacial acetic acid and the poly-second of 1.1g will be added after solution A, B, C mix homogeneously Enol, stirs 2h, forms the solution D of clarification；The solution D of clarification is carried out under voltage 20kv and flow rate 1.2mL/h Electrostatic spinning；The electrostatic spinning product obtained is put in 90 DEG C of oven drying 4h；By dried electrostatic spinning product transfer In Muffle furnace, sinter 3h at 800 DEG C, obtain lithium ionic cell cathode material lithium titanate sodium NaLiTiO3Nano wire.
Embodiment 3
By the NaCH of 0.15mmol3COO is dissolved in 2mL dimethylformamide (DMF), forms solution A；By 0.15mmol LiNO3It is dissolved in 5mL dehydrated alcohol, forms solution B；The isopropyl titanate of 0.45mmol is dissolved in dimethylformamide (DMF), solution C is formed；1.5mL glacial acetic acid and 1.2g polyvinyl alcohol will be added after solution A, B, C mix homogeneously, Stirring 2h, forms the solution D of clarification；The solution of clarification is carried out under voltage 18kv and flow rate 1.0mL/h electrostatic spinning； The electrostatic spinning product obtained is put in 80 DEG C of oven drying 4h；Dried electrostatic spinning product is transferred in Muffle furnace, Sinter 5h at 700 DEG C, obtain lithium ionic cell cathode material lithium titanate sodium NaLiTiO3Nano wire.
Embodiment 4
By the NaHCO of 0.15mmol3It is dissolved in 2mL dimethylformamide (DMF), forms solution A；By 0.2mmol LiCH3COO is dissolved in 5mL dehydrated alcohol, forms solution B；The isopropyl titanate of 0.50mmol is dissolved in 3mL bis- Methylformamide (DMF), forms solution C；1.5mL glacial acetic acid and 1.2 will be added after solution A, B, C mix homogeneously G polyvinyl alcohol, stirs 2h, forms the solution D of clarification；By the solution of clarification under voltage 16kv and flow rate 0.6mL/h Carry out electrostatic spinning；The electrostatic spinning product obtained is put in 90 DEG C of oven drying 4h；By dried electrostatic spinning product Transfer in Muffle furnace, sinter 6h at 600 DEG C, obtain lithium ionic cell cathode material lithium titanate sodium NaLiTiO3Nano wire.

Claims (3)

1. a sodium lithium titanate nano wire, it is characterised in that this sodium lithium titanate chemical formula is NaLiTiO3。
2. the preparation method of the sodium lithium titanate nano wire described in a claim 1, it is characterised in that described preparation method includes:
Sodium salt is dissolved in dimethylformamide (DMF), forms solution A；
Lithium salts is dissolved in dehydrated alcohol, forms solution B；
Titanium salt is dissolved in dimethylformamide (DMF), forms solution C；
After solution A, B, C mixing, add glacial acetic acid and macromolecule, stir 2h, form the solution D of clarification, solution D Middle Na, Li are 1:1:3～1:1.5:3.5 with the mol ratio of Ti element；
Solution D electrostatic spinning under 15～20kV voltages and 0.8～1.2mL/h flow rate by clarification；
The electrostatic spinning product obtained is put in 60～90 DEG C of oven drying 4h；
Dried electrostatic spinning product is transferred in Muffle furnace, sinters 3～6h at 600～800 DEG C, obtain metatitanic acid Lithium sodium nano wire.
The preparation method of sodium lithium titanate nano wire the most according to claim 2, it is characterised in that described sodium salt is NaCH3COO、NaHCO3In one or both compositions, described lithium salts is LiF, LiCH3COO and LiNO3 In a kind of or the most several compositionss, described titanium salt is isopropyl titanate, and described macromolecule is polyvinyl alcohol (PVA).
CN201610281086.9A 2016-04-29 2016-04-29 A kind of sodium lithium titanate nano wire and preparation method thereof Active CN105948108B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107119349A (en) * 2017-05-23 2017-09-01 宁波大学 A kind of carbon coating Na2Li2Ti6O14Nanofiber and preparation method thereof
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
CN115036468A (en) * 2022-05-26 2022-09-09 长虹三杰新能源有限公司 Sodium ion battery electrode material pre SEI film hard carbon material and application thereof

Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2000302547A (en) * 1999-02-16 2000-10-31 Toho Titanium Co Ltd Production of lithium titanate, lithium ion battery and its negative electrode
CN103633310A (en) * 2013-12-04 2014-03-12 上海电力学院 Sodium-ion battery anode material sodium lithium titanate and preparation method thereof
CN104201364A (en) * 2014-09-15 2014-12-10 李建明 Method for preparing spinel lithium titanate
CN104201341A (en) * 2014-08-26 2014-12-10 江苏科技大学 Preparation method of lithium titanate-nickel oxide nanofiber composite material for lithium battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000302547A (en) * 1999-02-16 2000-10-31 Toho Titanium Co Ltd Production of lithium titanate, lithium ion battery and its negative electrode
CN103633310A (en) * 2013-12-04 2014-03-12 上海电力学院 Sodium-ion battery anode material sodium lithium titanate and preparation method thereof
CN104201341A (en) * 2014-08-26 2014-12-10 江苏科技大学 Preparation method of lithium titanate-nickel oxide nanofiber composite material for lithium battery
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
C BELHOMME ET AL.: "Chemical and electrochemical behaviour of Ni-Ti in the cathodic conditions used in molten carbonate fuel cells", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107119349A (en) * 2017-05-23 2017-09-01 宁波大学 A kind of carbon coating Na2Li2Ti6O14Nanofiber and preparation method thereof
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
CN115036468A (en) * 2022-05-26 2022-09-09 长虹三杰新能源有限公司 Sodium ion battery electrode material pre SEI film hard carbon material and application thereof

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