CN111924879B - Method for preparing titanium niobate by using titanate as precursor - Google Patents

Method for preparing titanium niobate by using titanate as precursor Download PDF

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CN111924879B
CN111924879B CN202010896024.5A CN202010896024A CN111924879B CN 111924879 B CN111924879 B CN 111924879B CN 202010896024 A CN202010896024 A CN 202010896024A CN 111924879 B CN111924879 B CN 111924879B
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precursor
titanium niobate
ethanol
titanate
hydrochloric acid
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CN111924879A (en
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魏明灯
刘兴江
丁飞
余凌
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Fuzhou University
CETC 18 Research Institute
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CETC 18 Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • 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
    • 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
    • H01M4/483—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
    • C01P2002/00—Crystal-structural characteristics
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    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/40—Electric properties
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    • 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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Abstract

The invention discloses a method for preparing titanium niobate by taking titanate as a precursor, which comprises the steps of taking P25 and sodium hydroxide as raw materials and ethanol-water solution as a solvent, carrying out hydrothermal reaction, washing and drying to prepare a hydrogen-type titanate precursor, then carrying out secondary hydrothermal reaction on the obtained hydrogen-type titanate precursor and niobium pentachloride in ethanol solution of hydrochloric acid to prepare a titanium niobate precursor, and finally calcining the titanium niobate precursor in an inert gas environment at high temperature to prepare the titanium niobate. The method has the advantages of simple process, low cost and good repeatability, and the obtained titanium niobate has good electrochemical performance.

Description

Method for preparing titanium niobate by using titanate as precursor
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a method for preparing titanium niobate by using titanate as a precursor.
Background
The titanium niobate is considered to be a lithium battery cathode material with great commercial significance because of good structural stability, higher lithium embedding platform, low price and environmental friendliness. However, the existing preparation method of titanium niobate mainly uses organic titanium sources such as butyl titanate, isopropyl titanate and the like, and the cost is high, so that the large-scale application in actual life is limited. The invention provides a method for preparing titanium niobate by using titanate as a precursor, and no report related to low-cost preparation of titanium niobate by using titanate as a precursor exists at present.
Disclosure of Invention
The invention aims to provide a method for preparing titanium niobate by using titanate as a precursor.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing titanium niobate by using titanate as a precursor comprises the following steps:
(1) Respectively weighing P25 and sodium hydroxide according to the mass ratio of 1-2; after natural cooling, sequentially washing the obtained white precipitate with deionized water and 0.1mol/L hydrochloric acid solution until the pH value is 1 to 2, stirring in the 0.1mol/L hydrochloric acid solution for 24 hours, then centrifugally washing with deionized water until the pH value is 7, and finally drying in the air at 70 ℃ for 12 hours to obtain a hydrogen titanate precursor (HTO);
(2) Completely dissolving niobium pentachloride in an ethanol solution of hydrochloric acid (the volume ratio of the hydrochloric acid to the ethanol is 0.2 to 1) and then adding the hydrogen-type titanate precursor prepared in the step 1) into the ethanol solution of the hydrochloric acid according to the mass ratio of the niobium pentachloride to the hydrogen-type titanate precursor, stirring the mixture for 30 minutes, and carrying out hydrothermal reaction on the obtained mixed solution at 200 ℃ for 24 hours; after cooling to room temperature, centrifugally washing the product for 3 times by using ethanol, and drying at 70 ℃ to obtain a titanium niobate precursor;
(3) And (3) calcining the titanium niobate precursor obtained in the step (2) for 2 hours at 800 ℃ in an inert gas environment to obtain the final product Titanium Niobate (TNO).
The invention has the following remarkable advantages:
(1) The invention uses cheap P25 as titanium source, which reacts with concentrated alkali to obtain hydrogen type titanate precursor through simple proton exchange, then the hydrogen type titanate precursor reacts with niobium pentachloride at high temperature, and the product is calcined in inert gas environment to obtain the titanium niobate finally. The method has the advantages of simple process, low cost and good repeatability.
(2) The prepared titanium niobate serving as a lithium ion battery cathode material has high specific capacity and good cycling stability, and the capacity of the titanium niobate can still reach 197.7mAh/g after the titanium niobate is cycled for 200 circles under the condition that the current density is 5C (1C=396mAh/g). Even at a large current density of 20C, it still has a capacity of 142.2 mAh/g.
Drawings
FIG. 1 is an XRD pattern of the titanium niobate and hydrogen titanate precursors prepared in the examples.
FIG. 2 is an SEM photograph of titanium niobate prepared in example.
FIG. 3 is a graph of rate performance of a battery fabricated using the titanium niobate prepared in the example.
Fig. 4 is a graph comparing cycle performance of batteries manufactured using the titanium niobate prepared in examples.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Examples
(1) Adding 1g of P25 and 20g of sodium hydroxide into a mixed solution consisting of 25mL of ethanol and 25mL of water, stirring for 30 minutes, transferring the mixed solution into a 100mL of polytetrafluoroethylene lining, and carrying out hydrothermal reaction at 200 ℃ for 24 hours; after natural cooling, washing the obtained white precipitate with deionized water and 0.1mol/L hydrochloric acid solution in sequence until the pH value is 1 to 2, stirring in the 0.1mol/L hydrochloric acid solution for 24 hours, centrifugally washing with deionized water until the pH value is 7, and finally drying in the air at 70 ℃ for 12 hours to obtain a hydrogen titanate precursor (HTO);
(2) Completely dissolving 0.2g of niobium pentachloride in a mixed solution consisting of 1mL of hydrochloric acid and 30mL of ethanol, then adding 50mg of hydrogen type titanate precursor, stirring for 30 minutes, transferring the obtained mixed solution to 50mL of polytetrafluoroethylene lining, and carrying out hydrothermal reaction at 200 ℃ for 24 hours; after cooling to room temperature, centrifugally washing the product for 3 times by using ethanol, and drying at 70 ℃ to obtain a titanium niobate precursor;
(3) And (3) calcining the titanium niobate precursor obtained in the step (2) for 2 hours at 800 ℃ in an inert gas environment to obtain the final product Titanium Niobate (TNO).
Fig. 1 is an XRD chart of the titanium niobate and hydrogen-type titanate precursor prepared in this example. As can be seen in the figure, the hydrogen-type titanate precursor has no obvious diffraction peak and is amorphous titanate, while the diffraction peak of the titanium niobate is highly consistent with the PDF #13-0317 standard ratio card matching, and no other impurity phase exists.
FIG. 2 is an SEM image of the titanium niobate prepared in this example. As can be seen from the figure, the prepared titanium niobate is nanospheres stacked from small particles, which have a diameter of about 500nm.
Comparative example
(1) Completely dissolving 0.2g of niobium pentachloride in a mixed solution consisting of 1mL of hydrochloric acid and 30mL of ethanol, then adding 0.13mL of butyl titanate, stirring for 30 minutes, transferring the obtained mixed solution to a 50mL of polytetrafluoroethylene lining, and carrying out hydrothermal reaction at 200 ℃ for 24 hours; cooling to room temperature, centrifugally washing the product for 3 times by using ethanol, and drying at 70 ℃ to obtain a titanium niobate precursor (TBT);
(2) And (2) calcining the titanium niobate precursor obtained in the step (1) for 2 hours at 800 ℃ in an inert gas environment to obtain the final product Titanium Niobate (TNO).
Assembling the lithium ion battery: titanium niobate, acetylene black and sodium alginate are mixed according to the mass ratio of 70:20:10 is evenly coated on a copper foil after being mixed and ground to be used as a negative electrode, a reference electrode and a counter electrode are both made of metal lithium, and electrolyte is 1.0M LiPF 6 EC + DMC + EMC (EC/DMC/EMC =1/1/1 v/v) solution of (a). All assembly was performed in a glove box.
FIG. 3 is a graph of rate performance of a battery made from titanium niobate prepared in the example. As can be seen from the figure, the titanium niobate synthesized by the method has good rate capability, and still has the capacity of 142.2 mAh/g even under the large current density of 20C.
FIG. 4 is a graph showing the comparison of the cycle characteristics of the batteries made of titanium niobate obtained in examples and comparative examples. It can be seen from the figure that the battery prepared by using the titanium niobate obtained in the example has higher specific capacity and good cycling stability, and the capacity of the battery can still reach 197.7mAh/g after the battery is cycled for 200 circles under the condition that the current density is 5C (1C =396 mAh/g). Compared with the prior art, the capacity of the battery prepared by the titanium niobate obtained in the comparative example is only 165.5mAh/g after the battery is cycled for 200 circles under the same current density.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (1)

1. A method for preparing titanium niobate by taking titanate as a precursor is characterized by comprising the following steps: the method comprises the following steps:
(1) Adding P25 and sodium hydroxide into an ethanol-water solution, stirring for 30 minutes, and then carrying out hydrothermal reaction at 200 ℃ for 24 hours; after natural cooling, washing the obtained white precipitate with deionized water and 0.1mol/L hydrochloric acid solution in sequence until the pH value is 1 to 2, stirring in the 0.1mol/L hydrochloric acid solution for 24 hours, then centrifugally washing with deionized water until the pH value is 7, and finally drying in the air at 70 ℃ for 12 hours to obtain a hydrogen type titanate precursor;
(2) Completely dissolving niobium pentachloride in ethanol solution of hydrochloric acid, then adding the hydrogen type titanate precursor prepared in the step (1), stirring for 30 minutes, and carrying out hydrothermal reaction on the obtained mixed solution at 200 ℃ for 24 hours; after cooling to room temperature, centrifugally washing the product for 3 times by using ethanol, and drying at 70 ℃ to obtain a titanium niobate precursor;
(3) Calcining the titanium niobate precursor obtained in the step (2) for 2 hours at 800 ℃ in an inert gas environment to obtain a final product titanium niobate;
the mass ratio of the P25 to the sodium hydroxide used in the step (1) is 1 to 2; in the ethanol-water solution, the volume ratio of ethanol to water is 1;
the mass ratio of the niobium pentachloride to the hydrogen titanate precursor in the step (2) is 4 to 5; the volume ratio of the hydrochloric acid to the ethanol in the ethanol solution of the hydrochloric acid is 0.2 to 1.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010287496A (en) * 2009-06-12 2010-12-24 Mitsubishi Chemicals Corp Negative electrode material for nonaqueous electrolyte secondary battery, negative electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery using it
EP2909146A1 (en) * 2012-10-17 2015-08-26 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Method for preparing a titanium and niobium mixed oxide by solvothermal treatment; electrode and lithium accumulator comprising said mixed oxide
CN105633456A (en) * 2016-04-07 2016-06-01 南阳师范学院 Preparation method of lithium ion battery negative material titanium niobate
CN105776334A (en) * 2016-04-07 2016-07-20 南阳师范学院 Spherical Ti2Nb10O29 material and preparation method thereof
CN106025285A (en) * 2016-06-23 2016-10-12 南阳师范学院 Spherical titanium niobate electrode material and preparation method thereof
CN106169569A (en) * 2016-08-23 2016-11-30 复旦大学 A kind of preparation method of porous titanium niobate/carbon complex microsphere
CN109626418A (en) * 2018-12-17 2019-04-16 福州大学 A kind of method that topology conversion prepares titanium dioxide (B) nano wire
CN110571423A (en) * 2019-09-17 2019-12-13 上海理工大学 Preparation method of nitrogen-carbon-coated nano titanium niobate electrode material

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010287496A (en) * 2009-06-12 2010-12-24 Mitsubishi Chemicals Corp Negative electrode material for nonaqueous electrolyte secondary battery, negative electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery using it
EP2909146A1 (en) * 2012-10-17 2015-08-26 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Method for preparing a titanium and niobium mixed oxide by solvothermal treatment; electrode and lithium accumulator comprising said mixed oxide
CN105633456A (en) * 2016-04-07 2016-06-01 南阳师范学院 Preparation method of lithium ion battery negative material titanium niobate
CN105776334A (en) * 2016-04-07 2016-07-20 南阳师范学院 Spherical Ti2Nb10O29 material and preparation method thereof
CN106025285A (en) * 2016-06-23 2016-10-12 南阳师范学院 Spherical titanium niobate electrode material and preparation method thereof
CN106169569A (en) * 2016-08-23 2016-11-30 复旦大学 A kind of preparation method of porous titanium niobate/carbon complex microsphere
CN109626418A (en) * 2018-12-17 2019-04-16 福州大学 A kind of method that topology conversion prepares titanium dioxide (B) nano wire
CN110571423A (en) * 2019-09-17 2019-12-13 上海理工大学 Preparation method of nitrogen-carbon-coated nano titanium niobate electrode material

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