CN113299892B - Preparation method of iron-doped titanium dioxide/tungsten carbide lithium ion battery cathode material - Google Patents

Preparation method of iron-doped titanium dioxide/tungsten carbide lithium ion battery cathode material Download PDF

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CN113299892B
CN113299892B CN202110556132.2A CN202110556132A CN113299892B CN 113299892 B CN113299892 B CN 113299892B CN 202110556132 A CN202110556132 A CN 202110556132A CN 113299892 B CN113299892 B CN 113299892B
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titanium dioxide
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徐吉凯
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Huludao Minghao New Energy Materials Co ltd
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    • H—ELECTRICITY
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Abstract

The invention discloses a preparation method of an iron-doped titanium dioxide/tungsten carbide lithium ion battery cathode material, which comprises the steps of firstly hydrolyzing tetrabutyl titanate, doping iron into a titanium dioxide precursor in situ, and further stably immobilizing iron on the surface of titanium dioxide through hydrothermal reaction and hydrogen reduction calcination treatment; then mixing the titanium carbide with a tungsten salt solution, compounding the tungsten carbide and the iron-doped titanium dioxide together by oil bath heating and high-temperature calcination, and finally synthesizing an iron-doped titanium dioxide/tungsten carbide composite material with a large specific surface area, wherein the iron-doped titanium dioxide/tungsten carbide composite material is applied to a lithium ion battery cathode material and shows high lithium storage capacity.

Description

Preparation method of iron-doped titanium dioxide/tungsten carbide lithium ion battery cathode material
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a preparation method of an iron-doped titanium dioxide/tungsten carbide lithium ion battery cathode material.
Background
The rapid development of the lithium ion battery has made the lithium ion battery have achieved great success in portable electronic devices and automobiles, however, the rapid development of the electric vehicle industry is hindered by the problem of the lithium ion battery being too expensive. Therefore, the development of a lithium ion battery which is inexpensive and has excellent sustainable stability is still the focus of battery development. In recent years, titanium dioxide lithium ion battery negative electrode materials have been widely studied because titanium resources are abundant and titanium dioxide has low price and high chemical stability, but titanium dioxide has poor electronic conductivity, which greatly limits the electrochemical performance of titanium dioxide lithium ion batteries.
Disclosure of Invention
The invention mainly aims to solve the problems and provides a preparation method of an iron-doped titanium dioxide/tungsten carbide lithium ion battery cathode material, which has the characteristics of low cost, simple and convenient synthesis, excellent performance and the like and specifically comprises the following steps:
(1) under magnetic stirring, uniformly mixing an iron salt solution and an organic solvent, stirring for 10-20min, then dropwise adding tetrabutyl titanate at the rotating speed of 550-750rpm/min until a test solution is completely converted into colloidal precipitate, carrying out hydrothermal reaction, after the reaction is finished, washing, filtering and drying a product, then transferring the product into a tubular furnace, introducing hydrogen and calcining to obtain iron-doped titanium dioxide;
(2) mixing the iron-doped titanium dioxide prepared in the step (1) with ethanol, carrying out ultrasonic treatment for 10-30min, then adding tungsten chloride, stirring for 10-20min, then adding sodium thiosulfate, stirring for 1-3h, then transferring to an oil bath pot with a condensing device for heating, after the reaction is finished, cleaning the product with deionized water, filtering, drying, and then transferring to a tubular furnace filled with nitrogen for calcining, thus obtaining the iron-doped titanium dioxide/tungsten carbide material;
(3) And (3) mixing the iron-doped titanium dioxide/tungsten carbide material prepared in the step (2) with super conductive carbon and polyvinylidene fluoride according to the mass ratio of 8:1:1, then clockwise grinding under the action of N-methylpyrrolidone solvent until the mixture is ground into uniform slurry, then uniformly coating the slurry on an iron foil, drying at low temperature, placing the iron foil in a vacuum drying oven for drying for 12 hours, and finally cutting the iron-doped titanium dioxide/tungsten carbide lithium ion battery anode material into wafers by using a slicing machine to obtain the iron-doped titanium dioxide/tungsten carbide lithium ion battery anode material.
Preferably, the iron salt solution in step (1) is one of ferric chloride, ferric sulfate, ferric nitrate or ferric acetate, and the concentration is 2-10 mmol/L.
Preferably, the organic solvent in step (1) is one of xylene, toluene, n-pentane or diethyl ether.
Preferably, the mass-to-volume ratio of the ferric chloride solution, the organic solvent and the tetrabutyl titanate in the step (1) is (5-10) mL, (1-5) g.
Preferably, the hydrothermal reaction in step (1) is heating at the temperature of 150-200 ℃ for 12-24 h.
Preferably, the calcination in the step (1) is heating at a rate of 3 ℃/min, and calcining for 2h at a constant temperature of 300 ℃.
Preferably, the mass volume ratio of the iron-doped titanium dioxide to the ethanol in the step (2) is (0.5-2) g:50 mL.
Preferably, the molar ratio of the iron-doped titanium dioxide to the sodium thiosulfate and the tungsten chloride in the step (2) is 1 (0.25-2) to (0.005: 0.05).
Preferably, the oil bath heating in the step (2) is heating at 150-200 ℃ for 1-5 h.
Preferably, the calcination in step (2) is heating at a rate of 3 ℃/min, and calcining at a constant temperature of 1000 ℃ for 3h to 700-.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the invention provides a preparation method of an iron-doped titanium dioxide/tungsten carbide lithium ion battery cathode material, which has the advantages of easiness in preparation, low cost and the like.
(2) The iron-doped titanium dioxide/tungsten carbide material prepared by the invention is a composite material which is prepared by in-situ doping iron on the surface of titanium dioxide and compounding the iron and tungsten carbide, and not only provides a larger specific surface area for the titanium dioxide material, increases active sites for electrochemical reaction, and provides sufficient electron-ion transmission channels for the electrode material during working, so that lithium ions can be uniformly diffused in the structure; and the good conductivity of iron and tungsten carbide is utilized to improve the conductivity of the material, accelerate the transmission speed of electrons and be beneficial to the improvement of electrochemical performance.
Detailed Description
Example 1
The preparation of the iron-doped titanium dioxide/tungsten carbide lithium ion battery cathode material and the assembly of the lithium ion battery comprise the following steps:
(1) under magnetic stirring, uniformly mixing 10 mmol/L10 mL ferric chloride solution and 10mL toluene, stirring for 20min, dropwise adding 2g tetrabutyl titanate till the test solution is completely converted into colloidal precipitate, carrying out hydrothermal reaction at 180 ℃ for 24h, after the reaction is finished, washing, filtering and drying the product, transferring the product into a tubular furnace, introducing hydrogen, heating at the rate of 3 ℃/min, and calcining at the constant temperature of 300 ℃ for 2h to obtain iron-doped titanium dioxide;
(2) mixing 1g of the iron-doped titanium dioxide prepared in the step (1) with 50mL of ethanol, performing ultrasonic treatment for 30min, adding 0.15g of tungsten chloride, stirring for 10min, adding 2g of sodium thiosulfate, stirring for 3h, transferring to an oil bath pan with a condensing device, heating at 150 ℃ for 3h, after the reaction is finished, cleaning the product with deionized water, filtering, drying, transferring to a tubular furnace filled with nitrogen, heating at the rate of 3 ℃/min, and calcining at the constant temperature of 800 ℃ for 3h to obtain the iron-doped titanium dioxide/tungsten carbide material;
(3) And (3) mixing the iron-doped titanium dioxide/tungsten carbide material prepared in the step (2) with super conductive carbon and polyvinylidene fluoride according to the mass ratio of 8:1:1, then clockwise grinding under the action of N-methylpyrrolidone solvent until the mixture is ground into uniform slurry, then uniformly coating the slurry on an iron foil, drying at low temperature, placing the iron foil in a vacuum drying oven for drying for 12 hours, and finally cutting the iron-doped titanium dioxide/tungsten carbide lithium ion battery anode material into wafers by using a slicing machine to obtain the iron-doped titanium dioxide/tungsten carbide lithium ion battery anode material.
(4) And then sequentially assembling the positive electrode shell, the gasket, the lithium sheet, the electrolyte, the diaphragm, the electrolyte, the carbon/selenium-doped titanium dioxide lithium sulfur battery positive electrode sheet, the gasket and the negative electrode shell of the battery in an argon glove box, and finally sealing the battery by using a battery pressing machine for later use.
Example 2
The preparation of the iron-doped titanium dioxide/tungsten carbide lithium ion battery cathode material and the assembly of the lithium ion battery comprise the following steps:
(1) under magnetic stirring, uniformly mixing 5 mol/L10 mL ferric nitrate solution and 10mL dimethylbenzene, stirring for 20min, dropwise adding 3g tetrabutyl titanate until the test solution is completely converted into colloidal precipitate, carrying out hydrothermal reaction at 180 ℃ for 24h, after the reaction is finished, washing, filtering and drying the product, transferring the product into a tubular furnace, introducing hydrogen, heating at the rate of 3 ℃/min, and calcining at the constant temperature of 300 ℃ for 2h to obtain iron-doped titanium dioxide;
(2) Mixing 1g of the iron-doped titanium dioxide prepared in the step (1) with 50mL of ethanol, performing ultrasonic treatment for 30min, adding 0.15g of tungsten chloride, stirring for 10min, adding 2g of sodium thiosulfate, stirring for 3h, transferring to an oil bath pan with a condensing device, heating at 150 ℃ for 3h, after the reaction is finished, cleaning the product with deionized water, filtering, drying, transferring to a tubular furnace filled with nitrogen, heating at the rate of 3 ℃/min, and calcining at the constant temperature of 800 ℃ for 3h to obtain the iron-doped titanium dioxide/tungsten carbide material;
(3) and (3) mixing the iron-doped titanium dioxide/tungsten carbide material prepared in the step (2) with super conductive carbon and polyvinylidene fluoride according to the mass ratio of 8:1:1, then clockwise grinding under the action of N-methylpyrrolidone solvent until the mixture is ground into uniform slurry, then uniformly coating the slurry on an iron foil, drying at low temperature, placing the iron foil in a vacuum drying oven for drying for 12 hours, and finally cutting the iron-doped titanium dioxide/tungsten carbide lithium ion battery anode material into wafers by using a slicing machine to obtain the iron-doped titanium dioxide/tungsten carbide lithium ion battery anode material.
(4) And then sequentially assembling the positive electrode shell, the gasket, the lithium sheet, the electrolyte, the diaphragm, the electrolyte, the carbon/selenium-doped titanium dioxide lithium sulfur battery positive electrode sheet, the gasket and the negative electrode shell of the battery in an argon glove box, and finally sealing the battery by using a battery pressing machine for later use.
Comparative example 1
Comparative example 1 of the present invention is different from example 1 in that a titanium dioxide/tungsten carbide material was prepared without adding ferric chloride during the preparation process.
Comparative example 2
Comparative example 2 of the present invention is different from example 1 in that a titanium dioxide material was prepared without adding ferric chloride and tungsten carbide during the preparation process.
(1) Nitrogen adsorption desorption test (BET test)
The materials prepared in examples 1-2 and comparative examples 1-2 of the present invention were subjected to a nitrogen adsorption and desorption test to characterize the specific surface area of the material, and the specific steps were as follows: firstly, filling the material into a BET special test tube, then installing the BET special test tube on a degasser, opening a vacuum pump, and degassing for 12 hours at 110 ℃; after the degassing of the sample is finished, fixing the sample on a nitrogen adsorption and desorption instrument, and then starting the automatic nitrogen adsorption and desorption test in a liquid nitrogen environment. After the test is finished, the data of the specific surface area of the material can be obtained, and is specifically shown in table 1.
Table 1: specific surface area of the materials prepared in inventive examples 1-2 and comparative examples 1-2
Sample (I) Example 1 Example 2 Comparative example 1 Comparative example 2
Specific surface area (g/cm)2) 242.4 228.7 212.5 125.0
As can be seen from Table 1, the iron-doped titanium dioxide/tungsten carbide materials prepared in examples 1-2 of the present invention have a large specific surface area, which is, in turn, 242.4g/cm 2，228.7g/cm2. The materials prepared in examples 1-2 and the titanium dioxide/tungsten carbide material prepared in comparative example 1 have similar specific surface areas (212.5 g/cm) to those of comparative examples 1-22) However, the specific surface area of the iron-doped titanium dioxide/tungsten carbide material prepared in examples 1-2 of the present invention is approximately 2 times larger than that of the titanium dioxide material prepared in comparative example 2, which is also illustrated from the side that the iron-doped titanium dioxide/tungsten carbide material prepared in examples 1-2 of the present invention has a larger specific surface area because of the recombination of tungsten carbide, which increases the specific surface area of titanium dioxide and also provides more reactive sites, which is beneficial to the electrochemical reaction of the material.
(2) Electrochemical cycling Performance test
By adopting a blue battery tester, the batteries prepared in the embodiments 1-2 and the comparative examples 1-2 of the invention are subjected to charge and discharge cycle tests to represent the specific capacities of the batteries under different cycle times, and the specific steps are as follows: the battery is placed in a battery channel of a blue battery tester, program parameters of the blue battery tester are set, the theoretical specific capacity of the material is set to be 168mAh/g, the voltage testing interval is set to be 1.0-3.0V, the current density is set to be 168mA/g, and the charging and discharging testing times are set to be 500 times. After the test is finished, the data information of the cycle times and the specific capacity of the battery can be obtained from a blue battery system, the electrochemical cycle performance of the battery is further discussed by taking the specific discharge capacity of the battery as an example, and the specific data is shown in table 2.
Table 2: cycle Performance tables for materials prepared in inventive examples 1-2 and comparative examples 1-2
Figure BDA0003077225930000061
As can be seen from the data in Table 2, the first-turn specific discharge capacities of inventive example 1, inventive example 2, comparative example 1 and comparative example 2 were 294.1mAh/g, 261.4mAh/g, 196.3mAh/g and 132.5mAh/g, respectively; the 500-turn specific discharge capacities of the lithium ion battery are 181.3mAh/g, 172.5mAh/g, 70.3mAh/g and 62.5mAh/g respectively, so that compared with the materials prepared in comparative examples 1-2, the material prepared in the embodiment 1-in the invention has higher lithium storage capacity and good electrochemical cycle performance. The specific capacity of the materials prepared in the comparative examples 2 and 3 is greatly reduced along with the increase of the charging and discharging times, and even reduced to 62.5mAh/g, so that the influence of iron doping and molybdenum carbide compounding on the electrochemical performance of the titanium dioxide material is further illustrated, more reactive active sites are provided for the insertion and extraction of lithium ions, and the electrochemical reaction is facilitated.
(3) Electrochemical impedance spectroscopy test
Electrochemical impedance tests were performed on the batteries prepared in examples 1-2 and comparative examples 1-2 of the present invention using an electrochemical workstation to characterize the resistance between the electrode material and the electrolyte, comprising the following specific steps: the cell was placed in the cell holder of an electrochemical workstation and the automated test was started with an ac amplitude of 5mV and a frequency of 0.01Hz to 10kHz, the specific data for the resistance of which are shown in table 3.
Table 3: electrochemical impedance table of examples 1-2 of the present invention and comparative examples 1-2
Item Example 1 Example 2 Comparative example 1 Comparative example 2
Resistance (RC) 82Ω 79Ω 128Ω 201Ω
It can be observed from table 3 that the batteries prepared in examples 1-2 have smaller impedance values, which is because the iron doping and the tungsten carbide are compounded to improve the conductivity of the titanium dioxide and accelerate the transmission efficiency of electrons, which further verifies that the iron-doped titanium dioxide/tungsten carbide lithium ion battery cathode material has better electrochemical cycle performance.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. Such modifications and variations are considered to be within the scope of the invention.

Claims (10)

1. A preparation method of an iron-doped titanium dioxide/tungsten carbide lithium ion battery negative electrode material is characterized by comprising the following steps:
(1) under magnetic stirring, uniformly mixing an iron salt solution and an organic solvent, stirring for 10-20min, then dropwise adding tetrabutyl titanate at the rotation speed of 550-750rpm/min until a test solution is completely converted into colloidal precipitate, carrying out hydrothermal reaction, after the reaction is finished, washing, filtering and drying a product, then transferring the product into a tubular furnace, introducing hydrogen and calcining to obtain iron-doped titanium dioxide;
(2) Mixing the iron-doped titanium dioxide prepared in the step (1) with ethanol, carrying out ultrasonic treatment for 10-30min, then adding tungsten chloride, stirring for 10-20min, then adding sodium thiosulfate, stirring for 1-3h, then transferring to an oil bath pot with a condensing device for heating, after the reaction is finished, cleaning the product with deionized water, filtering, drying, and then transferring to a tubular furnace filled with nitrogen for calcining, thus obtaining the iron-doped titanium dioxide/tungsten carbide material;
(3) and (3) mixing the iron-doped titanium dioxide/tungsten carbide material prepared in the step (2) with super conductive carbon and polyvinylidene fluoride according to the mass ratio of 8:1:1, then clockwise grinding under the action of N-methylpyrrolidone solvent until the mixture is ground into uniform slurry, then uniformly coating the slurry on an iron foil, drying at low temperature, placing the iron foil in a vacuum drying oven for drying for 12 hours, and finally cutting the iron-doped titanium dioxide/tungsten carbide lithium ion battery anode material into wafers by using a slicing machine to obtain the iron-doped titanium dioxide/tungsten carbide lithium ion battery anode material.
2. The preparation method of the iron-doped titanium dioxide/tungsten carbide lithium ion battery anode material according to claim 1, wherein the iron salt solution in the step (1) is one of ferric chloride, ferric sulfate, ferric nitrate or ferric acetate, and the concentration of the iron salt solution is 2-10 mmol/L.
3. The method for preparing the iron-doped titanium dioxide/tungsten carbide lithium ion battery anode material according to claim 1, wherein the organic solvent in the step (1) is one of xylene, toluene, n-pentane or diethyl ether.
4. The preparation method of the iron-doped titanium dioxide/tungsten carbide lithium ion battery negative electrode material is characterized in that the mass-to-volume ratio of the iron salt solution, the organic solvent and the tetrabutyl titanate in the step (1) is (5-10) mL (1-5) g.
5. The method for preparing the iron-doped titanium dioxide/tungsten carbide lithium ion battery anode material as claimed in claim 1, wherein the hydrothermal reaction in step (1) is heating at a temperature of 150-200 ℃ for 12-24 h.
6. The preparation method of the iron-doped titanium dioxide/tungsten carbide lithium ion battery anode material according to claim 1, wherein the calcination in the step (1) is heating at a rate of 3 ℃/min to 300 ℃ and calcining at a constant temperature for 2 h.
7. The preparation method of the iron-doped titanium dioxide/tungsten carbide lithium ion battery anode material according to claim 1, wherein the mass-to-volume ratio of the iron-doped titanium dioxide to the ethanol in the step (2) is (0.5-2) g:50 mL.
8. The method for preparing the iron-doped titanium dioxide/tungsten carbide lithium ion battery negative electrode material as claimed in claim 1, wherein the molar ratio of the iron-doped titanium dioxide to the sodium thiosulfate and the tungsten chloride in the step (2) is 1 (0.25-2) to (0.005: 0.05).
9. The method for preparing the iron-doped titanium dioxide/tungsten carbide lithium ion battery anode material as claimed in claim 1, wherein the oil bath heating in step (2) is heating at 200 ℃ for 1-5 h.
10. The method for preparing the iron-doped titanium dioxide/tungsten carbide lithium ion battery anode material as claimed in claim 1, wherein the calcination in step (2) is heating at a rate of 3 ℃/min to 700-.
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