CN110571429A - Carbon-coated cobalt, titanium dioxide and lithium titanate composite material and preparation method thereof - Google Patents

Carbon-coated cobalt, titanium dioxide and lithium titanate composite material and preparation method thereof Download PDF

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Publication number
CN110571429A
CN110571429A CN201910883634.9A CN201910883634A CN110571429A CN 110571429 A CN110571429 A CN 110571429A CN 201910883634 A CN201910883634 A CN 201910883634A CN 110571429 A CN110571429 A CN 110571429A
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composite material
carbon
lithium
titanium dioxide
cobalt
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李星
刘语舟
毛孟凯
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Ningbo University
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Ningbo University
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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
    • H01M4/485—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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a carbon-coated cobalt, titanium dioxide and lithium titanate composite material and a preparation method thereof. The electrochemical performance test result of the composite material shows that the composite material has good electrochemical performance and has wide application prospect when being used as a negative electrode material of a lithium ion battery. In the whole preparation process, the operation is simple, the raw material cost is low, the investment is low, and the method is suitable for batch production.

Description

Carbon-coated cobalt, titanium dioxide and lithium titanate composite material and preparation method thereof
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a carbon-coated cobalt, titanium dioxide and lithium titanate composite material and a preparation method thereof.
Background
Currently, in order to solve the problems of energy exhaustion and environmental pollution, scientists are making efforts to research and develop clean energy sources such as solar energy, wind energy, biological energy, hydroenergy, geothermal energy, hydrogen energy, etc., and due to the intermittent, seasonal, regional and other disadvantages, the popularization and utilization are limited, so that a great deal of research is made on the aspects of energy conversion and storage to realize the high efficiency, environmental protection and utilization of renewable energy sources. Among them, the secondary lithium ion battery has excellent performance in energy storage and conversion devices, and has been widely paid attention by researchers. As a new and environmentally friendly renewable energy storage device, the lithium ion battery has been widely used as a power source for various electric devices, as small as various portable electronic devices such as mobile phones and notebook computers, and as large as vehicles such as electric automobiles and light rail cloud rails. In secondary lithium ion batteries and electrocatalysis reactions, efficient electrode materials and electrocatalysts are of great importance, ion migration paths can be shortened in electrode materials with nano structures, the migration rate of ions is improved, and active sites can be increased by means of large specific surface area to improve the electrochemical reaction activity of the materials. The one-dimensional nano material has the advantages of directional electron and ion conduction directions, short radial ion transmission path, strong stress bearing capacity, large electrochemical active surface area and the like, so that the one-dimensional nano material becomes an electrode material with a very promising prospect.
The electrostatic spinning technology is simple in operation and controllable in method, so that the electrostatic spinning technology is used for preparing various inorganic carbon-containing nano materials, such as carbon materials, metal oxides, phosphide, sulfides and other composite materials, has good conductivity and a rapid electron ion transmission path, and is widely used for secondary battery electrode materials. The electrostatic spinning technology is a method for preparing one-dimensional nanofibers by using electrostatic field force, and an electrostatic spinning device mainly comprises three parts: spinneret, high voltage power supply and fibre collection device. In the electrostatic spinning process, when high voltage is applied between a spinneret and a receiving plate, the solution sprayed from a needle is subjected to electrostatic field force and solution surface tension simultaneously, when the electrostatic field force and the surface tension of small liquid drops are balanced, a Taylor cone is formed at the needle, and when the voltage is increased continuously to enable the electrostatic field force of the liquid drops to be larger than the surface tension, the liquid drops are stretched into fibers and fall on the receiving plate under the action of the electrostatic field force to be collected. The morphology of electrospun fibers is mainly influenced by several factors: (1) system parameters such as molecular weight of polymer, conductivity, viscosity, dielectric constant, etc. of precursor solution; (2) operating parameters such as the gauge of the needle, voltage, flow rate, distance between the spinneret and the collection plate; (3) environmental parameters such as humidity, temperature, etc., and furthermore, parameters during annealing of the spun fiber (such as calcination temperature, calcination atmosphere, temperature rise rate) have a great influence on the structure, morphology, and electrochemical properties of the nanofiber material, and studies by Dan Li et al (advanced Materials,2004,16:1151-1170) have shown that the diameter of the spun fiber decreases as the voltage applied between the nozzle and the receiver and the receiving distance increases, and that the diameter of the spun fiber increases as the fluid Advance rate and the concentration of the polymer solution increase. The one-dimensional carbon nanofiber can be prepared by utilizing an electrostatic spinning technology and used as a lithium ion battery cathode material, and the electrochemical performance of the electrode material is favorably improved due to the advantages of simple operation, controllable appearance, good one-dimensional structure conductivity, large specific surface area and the like.
At present, the lithium ion battery cathode material commonly used in the market is mainly a carbon material, the carbon material comprises natural graphite, synthetic graphite, carbon fiber, mesophase spherule carbon and the like, and the theoretical specific capacity of the carbon is 372mAh g-1Carbon materials are widely used as negative electrode materials of commercial lithium ion batteries due to the advantages of low price, abundant resources and the like, but the graphite negative electrode battery can generate structural damage in the circulating process, an SEI (solid electrolyte interphase) film is easy to generate, irreversible capacity loss is caused by lithium precipitation, and the requirements of high multiplying power and long service life of the electrode materials are difficult to meet. TiO 22As a negative electrode material of the lithium ion battery, the material has the advantages of high discharge platform (1.7V), small volume expansion (less than 4 percent), low cost and environmental friendliness, and TiO is used for preparing a lithium ion battery2Has the advantages of high cycle efficiency and safety, charge and discharge rate, etc., however, TiO2has the disadvantage of poor self-conductivity, and as a negative electrode material, the performance of the material is limited by its electrochemical performance, Hanna He et al (Nano Energy, 20)18,44:217-227) coating TiO with carbon2The conductivity of (2) is improved. The elementary cobalt serving as the lithium ion cathode material has large volume change in the charging and discharging processes, and the material structure is easy to destroy and inactivate, so that large irreversible capacity is caused. Gaoran Li et al (Energy)&Environmental Science,2018,9:2372-2381) shows that the simple cobalt substance can effectively enhance the graphitization degree of carbon and improve the electrochemical performance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a carbon-coated cobalt, titanium dioxide and lithium titanate composite material and a preparation method thereof by combining an electrostatic spinning technology and a high-temperature sintering technology in the prior art.
the technical scheme adopted by the invention to solve the technical problems is as follows: a preparation method of a carbon-coated cobalt, titanium dioxide and lithium titanate composite material is characterized in that tetrabutyl titanate, cobalt acetate tetrahydrate and lithium acetate are used as raw materials by utilizing an electrostatic spinning technology, a proper amount of high molecules are added to be used as an adhesive, a spinning precursor solution is obtained after magnetic stirring for a section, an electrostatic spinning product is prepared by utilizing the electrostatic spinning technology under the condition of high voltage, and then N is placed in a tube furnace2Sintering in the atmosphere to obtain the carbon-coated cobalt, titanium dioxide and lithium titanate composite material, which specifically comprises the following steps:
(1) Weighing appropriate amount of cobalt acetate tetrahydrate (C)4H6CoO4·4H2O) and lithium acetate (CH)3COOLi), adding a certain amount of N, N-Dimethylformamide (DMF) and absolute ethyl alcohol, stirring for 1h, and adding a proper amount of PVP (K-120, polyvinylpyrrolidone) and tetrabutyl titanate (C)16H36O4Ti) and oxalic acid, and regulating the pH value to 1.5-2.5 by using glacial acetic acid; stirring for 10h to obtain a clear and transparent mixed solution as a spinning precursor solution;
(2) sucking the clear and transparent spinning precursor solution into an injector, wherein the distance between a needle head and a receiver is 16-20 cm under the voltage of 15-20 kV, and the flow rate is 1.2mL h-1Carrying out electrostatic spinning at the relative humidity of 20-30% and the temperature of 30-35 ℃ to obtain a spinning product;
(3) Drying the spinning product at the temperature of 80-100 ℃ for 5-8 h, transferring the spinning product into a tubular furnace, raising the temperature from room temperature to 200-350 ℃ through a program for 2-3 h in a nitrogen atmosphere, carrying out heat preservation and heating for 6h, raising the temperature to 650-750 ℃ through 6-8 h, sintering for 2-4 h, and slowly cooling to room temperature to obtain a carbon-coated cobalt, titanium dioxide and lithium titanate composite material;
The chemical formula of the lithium titanate is Li4Ti5O12；
The ratio of the amounts of cobalt, lithium, titanium and PVP in the precursor solution is 1 mol: 4 mol: 6 mol: 2g of the total weight of the mixture;
The solvents, reagents or raw materials for the reaction are all chemically pure.
The composite nanowire prepared by the invention can be used as a battery cathode material, and the specific discharge capacity can be maintained at 185.26 mAh.g after 100 times of charge-discharge cycle-1Above that, the coulombic efficiency can be maintained at 99.4%.
compared with the prior art, the carbon-coated composite material prepared by the electrostatic spinning technology has the following characteristics:
Li4Ti5O12、TiO2The combination of Co and C is favorable for improving the conductivity of the nano material and relieving Li4Ti5O12、TiO2The problem of poor conductivity per se; the carbon is coated on the material, so that the conductivity of the material is improved, the graphitization degree of the material is enhanced, and the electrochemical performance of the composite material is further improved; the composite material is in a nano-fiber shape, has the characteristics of large specific surface area and many active sites, is beneficial to the transmission of lithium ions in the material and is beneficial to improving the electrochemical performance of the material.
Drawings
FIG. 1 is an XRD pattern of a composite material made in accordance with the present invention;
FIG. 2 is an SEM image of the composite nano-material prepared by the invention;
FIG. 3 is a charge-discharge cycle chart of the composite material prepared by the invention as a lithium ion battery cathode material.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
Example 1
1.0mmoL (0.249g) cobalt acetate tetrahydrate and 4.0mmoL (0.264g) lithium acetate (C) were charged in a beaker2H3LiO2) Then, 5.0mL of N, N-Dimethylformamide (DMF) and 5.0mL of anhydrous ethanol were added, and the mixture was stirred for 60min to dissolve, and then 2g of PVP (K-120, polyvinylpyrrolidone) and 6.0mmol (2.05mL) of tetrabutyl titanate (C) were added16H36O4Ti), 2.0mmol (0.180) oxalic acid, adjusting pH to 1.5 with glacial acetic acid, stirring for 10h to obtain a clear and transparent mixed solution; injecting the clear and transparent mixed solution as a spinning precursor solution into an injector at a voltage of 15kV, wherein the vertical distance between a needle and a receiver is 16cm, and the flow rate is 1.2mL h-1Carrying out electrostatic spinning at the relative humidity of 20% and the temperature of 30 ℃; collecting the electrostatic spinning product, drying for 8h at 80 ℃, transferring the electrostatic spinning product into a porcelain boat, placing the porcelain boat in a tube furnace, introducing nitrogen at a constant speed, setting a heating program after the airflow is stable, raising the temperature from room temperature to 200 ℃ through 2h, preserving the heat for 6h to stabilize the fiber configuration, raising the temperature to 650 ℃ through 180min, preserving the heat for 240min, and naturally cooling to room temperature to obtain a black product.
The obtained black product is subjected to X-ray powder diffraction (XRD) test analysis, and the result shows that the corresponding characteristic diffraction peak and Li4Ti5O12、TiO2The characteristic diffraction peaks of Co correspond to each other (figure 1), that is, the black product is a carbon-coated cobalt, titanium dioxide and lithium titanate composite material. Scanning Electron Microscope (SEM) testing revealed that the morphology of the composite was nanofibrous (fig. 2). The obtained composite material is used as a lithium ion battery cathode material and is added at 100mA g-1The charge-discharge cycle performance of the material is tested under the current density, and the result shows that the discharge specific capacity of the material can be kept at 185.26 mAh.g after 100 times of charge-discharge cycle-1Above that, the coulombic efficiency can be maintained at 99.4%.
Example 2
1.0mmoL (0.249g) cobalt acetate tetrahydrate and 4.0mmoL (0.264g) lithium acetate (C) were charged in a beaker2H3LiO2) Then, 5.0mL of N, N-Dimethylformamide (DMF) and 5.0mL of anhydrous ethanol were added, and the mixture was stirred for 60min to dissolve, and then 2g of PVP (K-120, polyvinylpyrrolidone) and 6.0mmol (2.05mL) of tetrabutyl titanate (C) were added16H36O4Ti), 2.0mmol (0.180) oxalic acid, adjusting pH to 2.5 with glacial acetic acid, stirring for 10h to obtain clear and transparent mixed solution; injecting the clear and transparent mixed solution as a spinning precursor solution into an injector at a voltage of 20kV, wherein the vertical distance between a needle and a receiver is 20cm, and the flow rate is 1.2mL h-1Carrying out electrostatic spinning at 35 ℃ and with the relative humidity of 30%; collecting the electrostatic spinning product, drying at 100 ℃ for 5h, transferring the electrostatic spinning product into a porcelain boat, placing the porcelain boat in a tube furnace, introducing nitrogen at a constant speed, setting a heating program after the airflow is stable, heating from room temperature to 350 ℃ after 3h, preserving heat for 6h to stabilize the fiber configuration, heating to 750 ℃ after 240min, preserving heat for 120min, and naturally cooling to room temperature to obtain a black product. And carrying out X-ray powder diffraction (XRD) test analysis on the obtained black product, wherein the result shows that the black product is a carbon-coated cobalt, titanium dioxide and lithium titanate composite material. Scanning Electron Microscope (SEM) testing revealed that the morphology of the composite was. And (3) taking the obtained composite material as a lithium ion battery cathode material to carry out electrochemical performance test.
example 3
1.0mmoL (0.249g) cobalt acetate tetrahydrate and 4.0mmoL (0.264g) lithium acetate (C) were charged in a beaker2H3LiO2) Then, 5.0mL of N, N-Dimethylformamide (DMF) and 5.0mL of anhydrous ethanol were added, and the mixture was stirred for 60min to dissolve, and then 2g of PVP (K-120, polyvinylpyrrolidone) and 6.0mmol (2.05mL) of tetrabutyl titanate (C) were added16H36O4ti), 2.0mmol (0.180) oxalic acid, adjusting pH to 2.0 with glacial acetic acid, stirring for 10h to obtain clear and transparent mixed solution; injecting the clear and transparent mixed solution as a spinning precursor solution into an injector at a voltage of 18kV, wherein the vertical distance between a needle and a receiver is 18cm, and the flow rate is 1.2mL h-1Carrying out electrostatic spinning at the relative humidity of 25% and the temperature of 32 ℃; collecting electrostatic spinning product, drying at 90 deg.C for 7 hr, and transferringMoving the ceramic boat into a ceramic boat, placing the ceramic boat into a tube furnace, introducing nitrogen at a constant speed, setting a heating program after the airflow is stable, heating the ceramic boat from room temperature to 300 ℃ after 150min, preserving the heat for 6h to stabilize the fiber configuration, heating the ceramic boat to 700 ℃ after 210min, preserving the heat for 210min, and naturally cooling the ceramic boat to room temperature to obtain a black product. And carrying out X-ray powder diffraction (XRD) test analysis on the obtained black product, wherein the result shows that the black product is a carbon-coated cobalt, titanium dioxide and lithium titanate composite material. Scanning Electron Microscope (SEM) testing revealed that the morphology of the composite was. And (3) taking the obtained composite material as a lithium ion battery cathode material to carry out electrochemical performance test.

Claims (2)

1. A preparation method of a carbon-coated cobalt, titanium dioxide and lithium titanate composite material is characterized by comprising the following steps:
(1) weighing a proper amount of cobalt acetate-tetrahydrate and lithium acetate, adding a certain amount of N, N-dimethylformamide and absolute ethyl alcohol, stirring for 1h, adding a proper amount of PVP, tetrabutyl titanate and oxalic acid, and regulating the pH value to be 1.5-2.5 by using glacial acetic acid; stirring for 10h to obtain a clear and transparent mixed solution as a spinning precursor solution;
(2) sucking the clear and transparent spinning precursor solution into an injector, wherein the distance between a needle head and a receiver is 16-20 cm under the voltage of 15-20 kV, and the flow rate is 1.2mL h-1carrying out electrostatic spinning at the relative humidity of 20-30% and the temperature of 30-35 ℃ to obtain a spinning product;
(3) Drying the spinning product at the temperature of 80-100 ℃ for 5-8 h, transferring the spinning product into a tubular furnace, raising the temperature from room temperature to 200-350 ℃ through a program for 2-3 h in a nitrogen atmosphere, carrying out heat preservation and heating for 6h, raising the temperature to 650-750 ℃ through 6-8 h, sintering for 2-4 h, and slowly cooling to room temperature to obtain a carbon-coated cobalt, titanium dioxide and lithium titanate composite material;
The chemical formula of the lithium titanate is Li4Ti5O12；
The ratio of the amounts of cobalt, lithium, titanium and PVP in the precursor solution is 1 mol: 4 mol: 6 mol: 2g of the total weight of the mixture;
the solvents, reagents or raw materials for the reaction are all chemically pure.
2. The carbon-coated cobalt, titanium dioxide and lithium titanate composite material prepared by the preparation method of claim 1, which is characterized in that the composite material is used as a negative electrode material of a lithium ion battery, and has a specific discharge capacity of 185.26mAh g after 100 charge-discharge cycles under a certain current density-1Above, the coulombic efficiency remained at 99.4%.
CN201910883634.9A 2019-09-18 2019-09-18 Carbon-coated cobalt, titanium dioxide and lithium titanate composite material and preparation method thereof Pending CN110571429A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111540887A (en) * 2020-04-24 2020-08-14 宁波大学 Carbon-coated cobaltosic oxide and tin dioxide composite lithium battery material and preparation method thereof
CN115036489A (en) * 2022-06-27 2022-09-09 电子科技大学 Preparation method of high-safety lithium storage material based on lithium titanate heterostructure

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CN102820460A (en) * 2012-08-20 2012-12-12 上海交通大学 Electrostatic spinning method for preparing rare-earth metal doped nanometer lithium titanate
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CN106252664A (en) * 2016-08-26 2016-12-21 浙江理工大学 A kind of super loose carbonization structure porous carbon nanofiber and electrostatic spinning carbonization manufacture method thereof
CN107706408A (en) * 2017-08-17 2018-02-16 中国第汽车股份有限公司 A kind of preparation method of nanofiber lithium titanate composite material
US20180277882A1 (en) * 2017-03-21 2018-09-27 Kabushiki Kaisha Toshiba Electrode structure, secondary battery, battery pack, and vehicle

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US20120305856A1 (en) * 2011-05-31 2012-12-06 Hefei Guoxuan High-Tech Power Energy Co., Ltd. METHOD FOR PREPARING Li4NbxTi5-xO12/C NANOCOMPOSITE AS AN ANODE MATERIAL FOR LI-ION BATTERIES
CN102386385A (en) * 2011-10-09 2012-03-21 北京科技大学 Preparation method of Li4Ti5O12-TiO2 composite electrode material
CN102820460A (en) * 2012-08-20 2012-12-12 上海交通大学 Electrostatic spinning method for preparing rare-earth metal doped nanometer lithium titanate
CN103531756A (en) * 2013-11-01 2014-01-22 北京化工大学 Carbon nanofiber loaded lithium titanate thin film materials and manufacturing method thereof
CN105375018A (en) * 2015-10-23 2016-03-02 济南大学 Preparation method of bead chain-shaped lithium titanate fiber and obtained product
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111540887A (en) * 2020-04-24 2020-08-14 宁波大学 Carbon-coated cobaltosic oxide and tin dioxide composite lithium battery material and preparation method thereof
CN111540887B (en) * 2020-04-24 2021-05-14 宁波大学 Carbon-coated cobaltosic oxide and tin dioxide composite lithium battery material and preparation method thereof
CN115036489A (en) * 2022-06-27 2022-09-09 电子科技大学 Preparation method of high-safety lithium storage material based on lithium titanate heterostructure
CN115036489B (en) * 2022-06-27 2023-11-17 电子科技大学 Preparation method of lithium storage material based on lithium titanate heterostructure

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