CN111710853A - Monodisperse TiO for lithium ion battery cathode2Method for preparing nanoparticles - Google Patents

Monodisperse TiO for lithium ion battery cathode2Method for preparing nanoparticles Download PDF

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CN111710853A
CN111710853A CN202010481268.7A CN202010481268A CN111710853A CN 111710853 A CN111710853 A CN 111710853A CN 202010481268 A CN202010481268 A CN 202010481268A CN 111710853 A CN111710853 A CN 111710853A
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analytically pure
battery
tio
drying
film
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张炳辉
吴聪
王海
李存军
王林江
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Guilin University of Technology
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Guilin University of Technology
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    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a monodisperse TiO used for a lithium ion battery cathode2A method for preparing nanoparticles. Stirring ethanol and formic acid uniformly; adding sodium dodecyl benzene sulfonate, stirring, adding tetrabutyl titanate, and stirring uniformly; transferring the mixture into an autoclave; sealing, keeping the temperature, and cooling to room temperature; centrifuging, washing and drying the suspended substance; coating the powder and deionized water on a copper foil to form a film, and drying to prepare a working electrode; using metal lithium foil as a counter electrode, and adding LiPF6Dissolved in ethylene carbonate, dimethyl carbonate and methyl ethylene carbonateUsing a non-aqueous mixed solution of ester as an electrolyte, using a porous polypropylene film as a diaphragm, and assembling the battery in a glove box filled with argon; carrying out a first charge-discharge test on the battery; disassembling the battery after first charging and discharging, and cleaning the working electrode with absolute ethyl alcohol to obtain monodisperse TiO2And (3) nano-particle powder. The synthesis process is adjustable and controllable, the operation is simple and convenient, the cost is low, and the energy consumption is low.

Description

For negative electrode of lithium ion batteryMonodisperse TiO2Method for preparing nanoparticles
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to monodisperse TiO for a lithium ion battery cathode2A method for preparing nanoparticles.
Background
Nano TiO 22The material has good chemical stability, thermal stability and nontoxicity, and can be widely applied to the fields of ultraviolet resistant materials, textiles, photocatalytic catalysts, lithium ion batteries and the like. Thus, nano TiO2Becomes a hot spot of wide attention and is a nano material with the widest application prospect at present. Recent studies have shown that TiO is formed as a result of lithiation2Nanoparticles (Li)xTiO2X is more than or equal to 0 and less than or equal to 1) can increase the conductivity of the negative electrode material in the lithiation process, so that TiO2Nanoparticles are considered to be one of the best candidates for negative electrode materials for lithium ion batteries. However, it should be noted that TiO2The nanoparticles are used alone or as additives with the proviso that agglomeration of the nanoparticles cannot occur. However, nano TiO2In the form of individual particles and high surface activity of the nanoparticles, resulting in TiO2Strong chemical forces exist from nanoparticle to particle. Thus, TiO2The nano particles are used as the negative electrode of the lithium ion battery, and the dispersion of the nano particles is particularly important.
At present, TiO2The dispersion of the nanoparticles is usually achieved by adjusting the pH value of the aqueous solution and adding a suitable electrolyte or a polymeric surfactant, such as polyacrylamide, polymethacrylic acid, etc. Although the above method may serve to disperse TiO2The function of the nano particles, but the problems of complex technological process and difficult control exist. It is emphasized that, due to the above process, TiO2The surface of the nano-particles inevitably has chemical components which are not needed in the lithium ion battery, so that the secondary pollution on the surface of the particles is caused, and the obtained TiO is caused2Nanoparticles are difficult to be put into practical use in lithium ion batteries. Based on the above analysis, new tunable and controllable TiO are developed2The monodisperse nanoparticle process is importantScientific significance and practical significance.
Disclosure of Invention
The present invention is directed to solving the above problems of the prior art, and provides a monodisperse TiO for a negative electrode of a lithium ion battery2A method for preparing nanoparticles.
The method comprises the following specific steps:
(1) 20-30 ml of analytically pure ethanol and 20-30 ml of analytically pure formic acid are poured into a beaker and stirred vigorously for 20-30 minutes until mixed uniformly.
(2) Adding 0.5-1.5 g of analytically pure sodium dodecyl benzene sulfonate into the mixed solution obtained in the step (1), continuing to stir for 20-30 minutes, after uniform mixing, adding 20-30 ml of analytically pure tetrabutyl titanate, and continuing to stir strongly for 20-30 minutes until uniform mixing is achieved.
(3) The solution obtained in step (2) was transferred to a 100-200 ml teflon lined autoclave. The autoclave was sealed and kept at 180 ℃ for 12 hours in a drying oven and then naturally cooled to room temperature.
(4) And (4) taking out the suspended substance in the reactor in the step (3), centrifuging, washing 3 times by using deionized water and absolute ethyl alcohol, drying at 60 ℃ for 6 hours, and collecting a sample for later use.
(5) And (4) coating the powder obtained in the step (4) and deionized water on a copper foil according to a mass ratio of 70:30 to form a film, and drying the film in a vacuum environment at 120 ℃ to prepare the working electrode. Using metal lithium foil as a counter electrode, and adding 1 mol/L LiPF6The cells were assembled in a glove box filled with argon gas using a porous polypropylene (Celgard 2400) film as a separator, dissolved in a nonaqueous solution of analytically pure ethylene carbonate, analytically pure dimethyl carbonate and analytically pure methyl ethyl carbonate (in a volume of 1:1:1) as an electrolyte.
(6) And (4) carrying out a first charge-discharge test on the battery obtained in the step (5) within a voltage range of 0.01-2.5V.
(7) Disassembling the battery subjected to the first charge and discharge in the step (6), and cleaning the working electrode by using absolute ethyl alcohol to obtain the monodisperse TiO2And (3) nano-particle powder.
The synthesis process is adjustable and controllable, the operation is simple and convenient, the cost is low, and the energy consumption is low.
Drawings
FIG. 1 is an X-ray diffraction pattern of example 1.
FIG. 2 is a transmission electron micrograph of example 1.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1:
monodisperse TiO for lithium ion battery cathode2A method for preparing nanoparticles, comprising the steps of:
(1) 20 ml of analytically pure ethanol and 20 ml of analytically pure formic acid were poured into a beaker and stirred vigorously for 20-30 minutes until mixed well.
(2) Adding 0.5 g of analytically pure sodium dodecyl benzene sulfonate into the mixed solution obtained in the step (1), continuing to stir for 20-30 minutes, after uniform mixing, adding 20-30 ml of analytically pure tetrabutyl titanate, and continuing to stir strongly for 20-30 minutes until uniform mixing is achieved.
(3) The solution obtained in step (2) was transferred to a 100 ml teflon lined autoclave. The autoclave was sealed and kept at 180 ℃ for 12 hours in a drying oven and then naturally cooled to room temperature.
(4) And (4) taking out the suspended substance in the reactor in the step (3), centrifuging, washing 3 times by using deionized water and absolute ethyl alcohol, drying at 60 ℃ for 6 hours, and collecting a sample for later use.
(5) And (4) coating the powder obtained in the step (4) and deionized water on a copper foil according to a mass ratio of 70:30 to form a film, and drying the film in a vacuum environment at 120 ℃ to prepare the working electrode. Using metal lithium foil as a counter electrode, and adding 1 mol/L LiPF6The cells were assembled in an argon-filled glove box using a porous polypropylene (Celgard 2400) film as a separator, dissolved in a nonaqueous solution of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate (1: 1:1 by volume) as an electrolyte.
(6) And (4) carrying out a first charge-discharge test on the battery obtained in the step (5) within a voltage range of 0.01-2.5V.
(7) Disassembling the battery subjected to the first charge and discharge in the step (6), and cleaning the working electrode by using absolute ethyl alcohol to obtain the monodisperse TiO2And (3) nano-particle powder.
Example 2:
monodisperse TiO for lithium ion battery cathode2A method for preparing nanoparticles, comprising the steps of:
(1) 30 ml of analytically pure ethanol and 30 ml of analytically pure formic acid were poured into a beaker and stirred vigorously for 20-30 minutes until mixed well.
(2) Adding 1.5 g of analytically pure sodium dodecyl benzene sulfonate into the mixed solution obtained in the step (1), continuing to stir for 20-30 minutes, after uniform mixing, adding 20-30 ml of analytically pure tetrabutyl titanate, and continuing to stir strongly for 20-30 minutes until uniform mixing is achieved.
(3) The solution obtained in step (2) was transferred to a 100 ml teflon lined autoclave. The autoclave was sealed and kept at 180 ℃ for 12 hours in a drying oven and then naturally cooled to room temperature.
(4) And (4) taking out the suspended substance in the reactor in the step (3), centrifuging, washing 3 times by using deionized water and absolute ethyl alcohol, drying at 60 ℃ for 6 hours, and collecting a sample for later use.
(5) And (4) coating the powder obtained in the step (4) and deionized water on a copper foil according to a mass ratio of 70:30 to form a film, and drying the film in a vacuum environment at 120 ℃ to prepare the working electrode. Using metal lithium foil as a counter electrode, and adding 1 mol/L LiPF6The cells were assembled in a glove box filled with argon gas using a porous polypropylene (Celgard 2400) film as a separator, dissolved in a nonaqueous solution of analytically pure ethylene carbonate, analytically pure dimethyl carbonate and analytically pure methyl ethyl carbonate (in a volume of 1:1:1) as an electrolyte.
(6) And (4) carrying out a first charge-discharge test on the battery obtained in the step (5) within a voltage range of 0.01-2.5V.
(7) Disassembling the battery subjected to the first charge and discharge in the step (6), and cleaning the working electrode by using absolute ethyl alcohol to obtain the monodisperse TiO2And (3) nano-particle powder.

Claims (1)

1. Monodisperse TiO for lithium ion battery cathode2The preparation method of the nano-particles is characterized by comprising the following specific steps:
(1) pouring 20-30 ml of analytically pure ethanol and 20-30 ml of analytically pure formic acid into a beaker, and intensively stirring for 20-30 minutes until the mixture is uniform;
(2) adding 0.5-1.5 g of analytically pure sodium dodecyl benzene sulfonate into the mixed solution obtained in the step (1), continuing to stir for 20-30 minutes, after uniform mixing, adding analytically pure tetrabutyl titanate, continuing to stir strongly for 20-30 minutes until uniform mixing is achieved;
(3) transferring the solution obtained in the step (2) into a 100-200 ml Teflon-lined autoclave; sealing the autoclave, preserving the heat for 12 hours at 180 ℃ in a drying oven, and naturally cooling to room temperature;
(4) taking out the suspended matters in the reactor in the step (3), centrifuging, washing for 3 times by using deionized water and absolute ethyl alcohol, drying for 6 hours at 60 ℃, and collecting a sample for later use;
(5) coating the powder obtained in the step (4) and deionized water on a copper foil according to a mass ratio of 70:30 to form a film, and drying the film in a vacuum environment at 120 ℃ to prepare a working electrode; using metal lithium foil as a counter electrode, and adding 1 mol/L LiPF6Dissolving in nonaqueous solution of analytically pure ethylene carbonate, analytically pure dimethyl carbonate and analytically pure methyl ethyl carbonate with the volume of 1:1:1 as electrolyte, adopting porous polypropylene (Celgard 2400 film) as a diaphragm, and assembling the battery in a glove box filled with argon;
(6) carrying out a first charge-discharge test on the battery obtained in the step (5) within a voltage range of 0.01-2.5V;
(7) disassembling the battery subjected to the first charge and discharge in the step (6), and cleaning the working electrode by using absolute ethyl alcohol to obtain the monodisperse TiO2And (3) nano-particle powder.
CN202010481268.7A 2020-05-31 2020-05-31 Monodisperse TiO for lithium ion battery cathode2Method for preparing nanoparticles Pending CN111710853A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101348938A (en) * 2008-09-02 2009-01-21 济南大学 Preparation of nano barium titanate powder
CN103151507A (en) * 2013-03-12 2013-06-12 余颖 Preparation method of high-property lithium ion battery cathode material Li4Ti5O12
CN104362323A (en) * 2014-10-31 2015-02-18 天津大学 Method for quickly preparing lithium ion battery anode material by one-step solvent hot process
CN104743609A (en) * 2015-03-25 2015-07-01 中国科学院苏州纳米技术与纳米仿生研究所 Method for preparing transition metal oxide microspheres with controllable morphology
CN110790306A (en) * 2018-08-01 2020-02-14 北京化工大学 Preparation method of monodisperse anatase nano titanium dioxide transparent liquid phase dispersion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101348938A (en) * 2008-09-02 2009-01-21 济南大学 Preparation of nano barium titanate powder
CN103151507A (en) * 2013-03-12 2013-06-12 余颖 Preparation method of high-property lithium ion battery cathode material Li4Ti5O12
CN104362323A (en) * 2014-10-31 2015-02-18 天津大学 Method for quickly preparing lithium ion battery anode material by one-step solvent hot process
CN104743609A (en) * 2015-03-25 2015-07-01 中国科学院苏州纳米技术与纳米仿生研究所 Method for preparing transition metal oxide microspheres with controllable morphology
CN110790306A (en) * 2018-08-01 2020-02-14 北京化工大学 Preparation method of monodisperse anatase nano titanium dioxide transparent liquid phase dispersion

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIE WANG 等: "Porous TiO2(B)/anatase microspheres with hierarchical nano and microstructures for high-performance lithium-ion batteries", 《ELECTROCHIMICA ACTA》 *

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Application publication date: 20200925