CN111430704A - Fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material and preparation method and application thereof - Google Patents
Fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material as well as a preparation method and application thereof, wherein the method comprises the following steps: (1) mixing a nickel-containing material, a cobalt-containing material, a manganese-containing material, N-methyl pyrrolidone and polyvinylidene fluoride with stirring, and then standing to obtain a mixed glue solution; (2) carrying out electrostatic spinning on the mixed glue solution, and then drying to obtain a fiber rod-shaped precursor; (3) and carrying out high-temperature annealing on the fiber rod-shaped precursor so as to obtain the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material. Therefore, the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material obtained by the method has excellent stability and conductivity in the charging and discharging process, the service life of the battery is prolonged, and the synthesis method is simple and efficient, has low production cost and is beneficial to industrial production.
Description
Technical Field
The invention belongs to the field of lithium batteries, and particularly relates to a fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material and a preparation method and application thereof.
Background
In the energy storage system of China, chemical energy sources such as coal, petroleum and the like are mainly used as main energy sources, and hydroelectric power, nuclear power, solar energy, tidal energy, geothermal energy and the like are assisted. With the decreasing of non-renewable fossil energy and the environmental issues brought by fuels, the proportion of renewable green energy in energy systems is increasing. However, hydropower is limited in geographical position, and solar energy and wind energy also have intermittent characteristics, so that a new challenge is brought to the storage of electric energy. The traditional energy storage equipment can not meet the current requirement on energy storage, and the lithium ion battery is regarded as an energy storage system with the most application prospect due to the characteristics of higher working voltage (3.6-3.7V), higher energy density, no memory effect, small self-discharge and the like. Meanwhile, there is a higher demand for lithium ion batteries, i.e. the electric vehicles need longer driving range, which means that the batteries need to achieve higher energy density, and the capacity and energy density of the single batteries depend on the anode material to a great extent. The current relatively mature anode material comprises ternary materials of lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate and lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate, wherein the ternary anode material combines the good cycle stability of the lithium cobaltate, the high specific capacity of the lithium nickelate and the high safety and low cost of the lithium manganate, and becomes a material with great development prospect. The synthesis method of the ternary material generally comprises a coprecipitation method, a sol-gel method, a hydrothermal/solvothermal method, microwave synthesis, a high-temperature solid phase method and the like, but in general, firstly, a precursor is prepared, and the ternary material is obtained by sintering, so that the key for synthesizing the ternary precursor into the synthetic ternary material with high efficiency is provided. When the sol-gel method is used for synthesizing the superfine ternary material, the requirement on controlling the sintering temperature in the later period is strict in order to prevent agglomeration in the sintering process; the hydrothermal/solvothermal method can controllably prepare a material having a regular shape, but the synthesis efficiency is low, and is not suitable for mass production. Therefore, most of the current industrialized synthesis of ternary materials is coprecipitation to obtain a precursor, and then sintering is carried out for multiple times to obtain the ternary material with cladding and doping. Although the method is suitable for mass production, the synthesized ternary material has the problems of large element segregation, complex sintering process, high energy consumption and the like.
Therefore, the existing technology for synthesizing the cathode material is in need of improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material, and a preparation method and application thereof.
In one aspect of the invention, the invention provides a method for preparing a fluorocarbon co-doped nickel cobalt lithium manganate cathode material. According to an embodiment of the invention, the method comprises:
(1) mixing a nickel-containing material, a cobalt-containing material, a manganese-containing material, N-methyl pyrrolidone and polyvinylidene fluoride with stirring, and then standing to obtain a mixed glue solution;
(2) carrying out electrostatic spinning on the mixed glue solution, and then drying to obtain a fiber rod-shaped precursor;
(3) according to the method for preparing the fluorocarbon Co-doped nickel cobalt lithium manganate positive electrode material, a nickel-containing material, a cobalt-containing material, a manganese-containing material, N-methyl pyrrolidone and polyvinylidene fluoride are mixed, and then the mixture is kept stand to obtain the mixed glue solution.
In addition, the method for preparing the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material according to the embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, the nickel-containing material, the cobalt-containing material, the manganese-containing material, the N-methylpyrrolidone, and the polyvinylidene fluoride are mixed in a molar ratio of (0.1 to 0.5): (0.0125-0.0625): (0.0125-0.0625): (0.1-0.5): (0.01-0.05) mixing.
In some embodiments of the invention, in step (1), the nickel-containing material is at least one of nickel acetate, nickel carbonate, nickel oxalate and nickel oxide.
In some embodiments of the invention, in step (1), the cobalt-containing material is at least one of cobalt acetate, cobalt carbonate, cobalt oxalate and cobalt oxide.
In some embodiments of the invention, in step (1), the manganese-containing material is at least one of manganese acetate, manganese carbonate, manganese oxalate and manganese oxide.
In some embodiments of the present invention, in the step (2), the electrostatic spinning conditions include a nozzle aperture of 500 to 800 μm, a feeding speed of 0.2 to 0.8m L/h, a voltage of 20 to 40kV, a solidification distance between the nozzle and the collector of 15 to 35cm, and a pressure of 0.3 to 0.5 MPa.
In some embodiments of the present invention, in the step (2), the diameter of the fiber rod-shaped precursor is 20 to 150 nm.
In some embodiments of the invention, in step (3), the high temperature annealing conditions are: heating from 25 ℃ to 400 ℃ at a rate of 1-10 ℃/min and preserving heat for 2-4h, then heating to 700-900 ℃ at a rate of 1-10 ℃/min and preserving heat for 10-16h, and then cooling to room temperature along with the furnace.
In a second aspect of the invention, the invention provides a fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material. According to the embodiment of the invention, the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material is prepared by adopting the method. Therefore, the cathode material has high capacity and excellent stability and electrochemical performance.
In a third aspect of the present invention, a lithium battery is provided. According to an embodiment of the present invention, the lithium battery has the above-described positive electrode material. Therefore, the lithium battery has excellent cycle stability and rate capability.
In a fourth aspect of the invention, an energy storage device is presented. According to an embodiment of the present invention, the energy storage device has the lithium battery described above. Therefore, the energy storage device loaded with the lithium battery with excellent cycle stability and rate capability has excellent energy storage capacity, so that the use requirement of consumers is met.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic flow chart of a method for preparing a fluorocarbon co-doped nickel cobalt lithium manganate cathode material according to an embodiment of the present invention;
FIG. 2 is an SEM spectrum of a fiber rod-like precursor obtained in example 1;
fig. 3 is a comparison graph of cycle performance of a battery assembled by taking the fluorocarbon co-doped lithium nickel cobalt manganese oxide positive electrode material obtained in example 1 and the lithium nickel cobalt manganese oxide positive electrode material (undoped fluorocarbon) obtained by electrostatic spinning as the positive electrode material.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, the invention provides a method for preparing a fluorocarbon co-doped nickel cobalt lithium manganate cathode material. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: mixing nickel-containing material, cobalt-containing material, manganese-containing material, N-methyl pyrrolidone and polyvinylidene fluoride, and standing
In the step, mixing a nickel-containing material, a cobalt-containing material, a manganese-containing material, N-methyl pyrrolidone and polyvinylidene fluoride can comprise the steps of firstly dissolving the nickel-containing material, the cobalt-containing material and the manganese-containing material in the N-methyl pyrrolidone, fully dissolving to obtain a mixed solution, then slowly adding the polyvinylidene fluoride into the mixed solution with stirring (the stirring speed is 280-400rpm), wherein the adding time is 20-40 minutes, after the adding is finished, the stirring speed is adjusted to be 500-1000rpm, stirring is carried out for 4-12 hours, then standing is carried out for 30-120 minutes to remove bubbles in the stirring process to obtain a mixed glue solution, or firstly, with stirring (the stirring speed is 280-400rpm), the polyvinylidene fluoride is slowly added into the N-methyl pyrrolidone, the adding time is 20-40 minutes, after the adding is finished, the stirring speed is adjusted to be 500-1000rpm, stirring is carried out for 4-12 hours to obtain a glue solution, then the nickel-containing material, the cobalt-containing material and the manganese-containing material are slowly added into the N-methyl pyrrolidone, the adding time is 15 minutes, the stirring speed is adjusted to be 500-1000rpm, the stirring speed after the adding is finished, the adding is carried out, the stirring speed is adjusted, the stirring speed is 1000rpm, the stirring speed is adjusted, the stirring speed is used as a high molecular chain of the stirring speed is used for 4-400 rpm, the stirring speed, the mixed glue solution, the stirring speed is used for obtaining a high molecular chain of the mixed glue solution, the high molecular chain of the high molecular.
The inventor finds that the higher the proportion of added polyvinylidene fluoride is, the higher the fluorine doping proportion of the obtained composite material is, the better the cycle stability of the material is, the better the electronic conductivity of the composite material is, and the rate performance of the composite electrode is improved, however, if the polyvinylidene fluoride is too high, L i-F bond energy is much higher than L i-O bond energy, so that the de-intercalation of L i is not beneficial, and the reversible capacity of the material is reduced, and the preferable nickel-containing material is at least one of nickel acetate, nickel carbonate, nickel oxalate and nickel chloride, and the preferable nickel-containing material is at least one of cobalt carbonate, cobalt oxalate and manganese chloride, and the preferable cobalt-containing material is at least one of cobalt acetate, cobalt oxalate and manganese chloride, and manganese acetate, and manganese chloride.
S200: the mixed glue solution is subjected to electrostatic spinning and then is dried
Preferably, the electrostatic spinning condition is that the aperture of a spray head is 500-0.8 m, the feeding speed is 0.2-0.8m L/h, the voltage is 20-40 kV, the curing distance between the spray head and a collector is 15-35cm, and the pressure is 0.3-0.5 MPa, the vacuum drying condition is that the oven temperature is 60-100 ℃ and the drying time is 8-12h, the diameter of the fiber rod-shaped precursor obtained in the step is 20-150 nm.
S300: high-temperature annealing of fiber rod-shaped precursor
In the step, the obtained fibrous precursor is annealed at a high temperature so as to obtain the fluorocarbon co-doped nickel cobalt lithium manganate cathode material. The inventor finds that a fiber rod-shaped precursor obtained by performing electrostatic spinning and drying on the mixed glue solution is subjected to high-temperature annealing to perform fluorocarbon element co-doping, namely, the fluorocarbon element co-doped lithium nickel cobalt manganese oxide material is realized by a one-step method, wherein the surface of the lithium nickel cobalt manganese oxide material can be modified by the fluorine element, the surface energy of the lithium nickel cobalt manganese oxide material is reduced, the corrosion of the material caused by the increase of lithium hydroxide and lithium carbonate due to high nickel content is inhibited, the stability of the surface of the material is improved, namely, the stability of a lithium nickel cobalt manganese oxide electrode in the charging and discharging cycle process is improved, and the cycle life of the battery is. Meanwhile, the carbon in-situ coating effectively optimizes the conductivity of the nickel cobalt lithium manganate material, and reduces the intrinsic resistance of the pole piece to a certain extent, so that the internal resistance of the thick electrode is greatly reduced, and the rate capability of the thick electrode is improved. Preferably, the high-temperature annealing conditions are as follows: heating from 25 ℃ to 400 ℃ at the speed of 1-10 ℃/min and preserving heat for 2-4h, then heating to 900 ℃ at the speed of 1-10 ℃/min and preserving heat for 10-16h, and then cooling to room temperature along with the furnace.
In a second aspect of the invention, the invention provides a fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material. According to the embodiment of the invention, the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material is prepared by adopting the method. Therefore, the cathode material has high capacity and excellent stability and electrochemical performance. It should be noted that the characteristics and advantages described above for the method for preparing the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material are also applicable to the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material, and are not described herein again.
In a third aspect of the present invention, a lithium battery is provided. According to an embodiment of the present invention, the lithium battery has the above-described positive electrode material. Therefore, the lithium battery has excellent cycle stability and rate capability. It should be noted that the characteristics and advantages described above for the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material and the preparation method thereof are also applicable to the lithium battery, and are not described herein again.
In a fourth aspect of the invention, an energy storage device is presented. According to an embodiment of the present invention, the energy storage device has the lithium battery described above. Therefore, the energy storage device loaded with the lithium battery with excellent cycle stability and rate capability has excellent energy storage capacity, so that the use requirement of consumers is met. It should be noted that the features and advantages described above for the lithium battery are also applicable to the energy storage device, and are not described herein again.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
(1) Dissolving 0.1mol of nickel acetate, 0.0125mol of cobalt acetate and 0.0125mol of manganese acetate in 0.3mol of N-methylpyrrolidone, fully dissolving to obtain a mixed solution, slowly adding 0.03mol of polyvinylidene fluoride into the mixed solution with mechanical stirring (the stirring speed is 350rpm), wherein the adding time is 30 minutes, adjusting the stirring speed to 800rpm after the adding is finished, stirring for 12 hours, and then standing for 30 minutes to remove bubbles in the stirring process to obtain a mixed glue solution;
(2) performing electrostatic spinning on the obtained mixed glue solution in a fume hood, discharging volatilized N-methyl pyrrolidone through an exhaust device, and performing vacuum drying to obtain a fiber rod-shaped precursor (refer to figure 2) with the diameter of 50-100nm, wherein the electrostatic spinning condition comprises that the aperture of a spray head is 500 mu m, the feeding speed is 0.8m L/h, the voltage is 20-40 kV, the curing distance between the spray head and a collector is 25cm, and the pressure is 0.4MPa, the vacuum drying condition is that the temperature of an oven is 100 ℃ and the drying time is 10 h;
(3) and (3) carrying out high-temperature annealing on the obtained fibrous precursor so as to obtain a fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material, wherein the high-temperature annealing condition is as follows: heating from 25 deg.C to 350 deg.C at a rate of 5 deg.C/min and holding for 2h, heating to 750 deg.C at a rate of 10 deg.C/min and holding for 10h, and furnace cooling to room temperature.
And (4) conclusion: x-ray photoelectron spectroscopy (XPS) and elemental analysis are performed on the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material obtained in example 1, and it can be seen that the positive electrode material contains carbon and fluorine elements, indicating that the positive electrode material obtained by the method is doped with fluorocarbon elements; the fluorocarbon co-doped lithium nickel cobalt manganese oxide positive electrode material obtained in example 1 and the lithium nickel cobalt manganese oxide positive electrode material obtained by electrostatic spinning (undoped carbon) were used respectivelyFluorine) as a positive electrode material, and a 12 mu m aluminum foil as a positive electrode current collector, and preparing a high-surface-density positive electrode plate with the single-surface-density of 31mg/cm2The lithium sheet is used as a negative electrode, EC/DMC (ethylene carbonate/dimethyl carbonate) is used as electrolyte, the content of lithium hexafluorophosphate is 1.0 mol/L, the battery is assembled, the obtained battery cycle performance curve is shown in fig. 3, the battery composed of the positive electrode material obtained in the example 1 has the first discharge capacity of 195.3mAh/g under the current density of 20mA/g, the capacity retention rate is 90.84% after 100 cycles, the battery composed of the nickel cobalt lithium manganate positive electrode material without fluorocarbon doping has the first discharge capacity of 190.6mAh/g under the current density of 20mA/g, the capacity retention rate is 38.33% after 100 cycles, furthermore, the rate test is carried out, the battery composed of the positive electrode material obtained in the example 1 has the reversible capacities of 195.3mAh/g, 185.2mAh/g, 179.1mAh/g, 173.2mAh/g, 166.5mAh/g, 183 mAh/g, 183.3.3 g, 183 mAh/g, and 183.3 g/g under the reversible capacities of the current density of the lithium manganate positive electrode material under the current density of 20mA/g and 20 mA/g.
Example 2
(1) Dissolving 0.1mol of nickel carbonate, 0.0125mol of cobalt carbonate and 0.0125mol of manganese carbonate in 0.4mol of N-methylpyrrolidone, fully dissolving to obtain a mixed solution, slowly adding 0.04mol of polyvinylidene fluoride into the mixed solution with mechanical stirring (the stirring speed is 400rpm), adding for 30min, adjusting the stirring speed to 800rpm after the addition is finished, stirring for 12h, and then standing for 30min to remove bubbles in the stirring process to obtain a mixed glue solution;
(2) carrying out electrostatic spinning on the obtained mixed glue solution in a fume hood, discharging volatilized N-methyl pyrrolidone through an exhaust device, and then carrying out vacuum drying to obtain a fiber rod-shaped precursor with the diameter of 50-120 nm, wherein the electrostatic spinning conditions comprise that the aperture of a spray head is 800 mu m, the feeding speed is 0.8m L/h, the voltage is 20-40 kV, the curing distance between the spray head and a collector is 25cm, and the pressure is 0.3MPa, the vacuum drying conditions comprise that the temperature of an oven is 100 ℃ and the drying time is 10 h;
(3) and (3) carrying out high-temperature annealing on the obtained fibrous precursor so as to obtain a fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material, wherein the high-temperature annealing condition is as follows: heating from 25 deg.C to 350 deg.C at a rate of 5 deg.C/min and holding for 2h, heating to 750 deg.C at a rate of 10 deg.C/min and holding for 10h, and furnace cooling to room temperature.
And (4) conclusion: x-ray photoelectron spectroscopy (XPS) and elemental analysis are performed on the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material obtained in example 2, and it can be seen that the positive electrode material contains carbon and fluorine elements, indicating that the positive electrode material obtained by the method is doped with fluorocarbon elements; the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material obtained in the example 2 is used as a positive electrode material, a 12 mu m aluminum foil is used as a positive electrode current collector, and the preparation of the high-surface-density positive electrode piece is carried out, wherein the single-surface-density of the electrode piece is 31mg/cm2The lithium sheet is used as a negative electrode, EC/DMC (ethylene carbonate/dimethyl carbonate) is used as electrolyte, the content of lithium hexafluorophosphate is 1.0 mol/L, the battery is assembled, the cycle performance curve of the battery shows that the battery composed of the positive electrode material obtained in the example 2 has a first discharge capacity of 191.5mAh/g under the current density of 20mA/g and a capacity retention rate of 85.84% after 100 cycles, and further a multiplying power test is carried out, and the reversible capacities of the battery composed of the positive electrode material obtained in the example 1 under the current densities of 20mA/g, 50mA/g, 100mA/g, 200mA/g and 500mA/g are 191.5mAh/g, 185.2mAh/g, 174.4mAh/g and 155.3mAh/g respectively.
Example 3
(1) Slowly adding 0.03mol of polyvinylidene fluoride into 0.3mol of N-methyl pyrrolidone with stirring (the stirring rotation speed is 280-400rpm), wherein the adding time is 25 minutes, after the adding is finished, the stirring rotation speed is adjusted to 750rpm, stirring is carried out for 12 hours to obtain a glue solution, then slowly adding 0.08mol of nickel oxalate, 0.01mol of cobalt oxalate and 0.01mol of manganese oxalate into the glue solution, wherein the adding time is 15 minutes, the stirring rotation speed is kept in the process, after the adding is finished, the stirring rotation speed is adjusted to 600rpm, stirring is carried out for 10 hours, and then standing is carried out for 30 minutes to remove bubbles in the stirring process to obtain a mixed glue solution
(2) Carrying out electrostatic spinning on the obtained mixed glue solution in a fume hood, discharging volatilized N-methyl pyrrolidone through an exhaust device, and then carrying out vacuum drying to obtain a fiber rod-shaped precursor with the diameter of 50-100nm, wherein the electrostatic spinning conditions comprise that the aperture of a spray head is 800 mu m, the feeding speed is 0.6m L/h, the voltage is 30kV, the curing distance between the spray head and a collector is 30cm, and the pressure is 0.5MPa, the vacuum drying conditions comprise that the temperature of an oven is 90 ℃ and the drying time is 12 h;
(3) and (3) carrying out high-temperature annealing on the obtained fibrous precursor so as to obtain a fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material, wherein the high-temperature annealing condition is as follows: heating from 25 deg.C to 300 deg.C at a rate of 2 deg.C/min and holding for 1h, heating to 750 deg.C at a rate of 5 deg.C/min and holding for 10h, and furnace cooling to room temperature.
And (4) conclusion: x-ray photoelectron spectroscopy (XPS) and elemental analysis were performed on the fluorocarbon-co-doped nickel cobalt lithium manganate positive electrode material obtained in example 3, and it was found that the positive electrode material contains carbon and fluorine elements, indicating that the positive electrode material obtained by the method is doped with fluorocarbon elements; the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material obtained in the example 3 is used as a positive electrode material, a 12 mu m aluminum foil is used as a positive electrode current collector, and the preparation of a high-surface-density positive electrode piece is carried out, wherein the single-surface-density of the electrode piece is 31mg/cm2The lithium sheet is used as a negative electrode, EC/DMC (ethylene carbonate/dimethyl carbonate) is used as electrolyte, the content of lithium hexafluorophosphate is 1.0 mol/L, the battery is assembled, the cycle performance curve of the battery shows that the battery composed of the positive electrode material obtained in the example 3 has the first discharge capacity of 192.8mAh/g under the current density of 20mA/g and the capacity retention rate of 88.23% after 100 cycles, and further, the reversible capacities of the battery composed of the positive electrode material obtained in the example 3 under the current densities of 20mA/g, 50mA/g, 100mA/g, 200mA/g and 500mA/g are 192.8mAh/g, 185.4mAh/g, 177.8mAh/g, 168.6mAh/g and 147.7mAh/g respectively.
Example 4
(1) Slowly adding 0.05mol of polyvinylidene fluoride into 0.5mol of N-methyl pyrrolidone along with stirring (the stirring rotation speed is 280-400rpm), wherein the adding time is 40 minutes, after the adding is finished, the stirring rotation speed is adjusted to 900rpm, stirring is carried out for 12 hours, so as to obtain a glue solution, then slowly adding 0.08mol of nickel chloride, 0.01mol of cobalt chloride and 0.01mol of manganese chloride into the glue solution, wherein the adding time is 25 minutes, the stirring rotation speed is kept in the process, after the adding is finished, the stirring rotation speed is adjusted to 750rpm, stirring is carried out for 12 hours, and then standing is carried out for 30 minutes so as to remove bubbles in the stirring process, so as to obtain a mixed glue solution;
(2) carrying out electrostatic spinning on the obtained mixed glue solution in a fume hood, discharging volatilized N-methyl pyrrolidone through an exhaust device, and then carrying out vacuum drying to obtain a fiber rod-shaped precursor with the diameter of 100-150 nm, wherein the electrostatic spinning conditions comprise that the aperture of a spray head is 800 mu m, the feeding speed is 0.8m L/h, the voltage is 25kV, the curing distance between the spray head and a collector is 15cm, and the pressure is 0.3MPa, the vacuum drying conditions comprise that the temperature of an oven is 100 ℃ and the drying time is 10 h;
(3) and (3) carrying out high-temperature annealing on the obtained fibrous precursor so as to obtain a fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material, wherein the high-temperature annealing condition is as follows: heating from 25 deg.C to 400 deg.C at 8 deg.C/min and holding for 2h, heating to 800 deg.C at 5 deg.C/min and holding for 10h, and cooling to room temperature.
And (4) conclusion: x-ray photoelectron spectroscopy (XPS) and elemental analysis are performed on the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material obtained in example 4, and it can be seen that the positive electrode material contains carbon and fluorine elements, indicating that the positive electrode material obtained by the method is doped with fluorocarbon elements; the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material obtained in the example 4 is used as a positive electrode material, a 12 μm aluminum foil is used as a positive electrode current collector, and the preparation of a high-surface-density positive electrode piece is carried out, wherein the single-surface-density of the electrode piece is 31mg/cm2The lithium sheet was used as the negative electrode, EC/DMC (ethylene carbonate/dimethyl carbonate) was used as the electrolyte, lithium hexafluorophosphate content was 1.0 mol/L, and the battery was assembled, from the obtained battery cycle performance curve, the battery composed of the positive electrode material obtained in example 4 had a first discharge capacity of 192.6mAh/g at a current density of 20mA/g and a capacity retention rate of 82.59% after 100 cycles, and further subjected to a rate test, and the battery composed of the positive electrode material obtained in example 4 had reversible capacities of 192.6mAh/g, 184.0 mA/g at 20mA/g, 50mA/g, 100mA/g, 200mA/g, and 500mA/g, respectivelyh/g、175.7mAh/g、166.0mAh/g、136.5mAh/g。
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The method for preparing the fluorocarbon co-doped nickel cobalt lithium manganate cathode material is characterized by comprising the following steps of:
(1) mixing a nickel-containing material, a cobalt-containing material, a manganese-containing material, N-methyl pyrrolidone and polyvinylidene fluoride with stirring, and then standing to obtain a mixed glue solution;
(2) carrying out electrostatic spinning on the mixed glue solution, and then drying to obtain a fiber rod-shaped precursor;
(3) and carrying out high-temperature annealing on the fiber rod-shaped precursor so as to obtain the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material.
2. The method according to claim 1, wherein in step (1), the nickel-containing material, the cobalt-containing material, the manganese-containing material, the N-methylpyrrolidone, and the polyvinylidene fluoride are mixed in a molar ratio (0.1-0.5): (0.0125-0.0625): (0.0125-0.0625): (0.1-0.5): (0.01-0.05) mixing.
3. The method according to claim 1 or 2, wherein in step (1), the nickel-containing material is at least one of nickel acetate, nickel carbonate, nickel oxalate and nickel oxide;
optionally, in step (1), the cobalt-containing material is at least one of cobalt acetate, cobalt carbonate, cobalt oxalate and cobalt oxide.
4. The method of claim 3, wherein in step (1), the manganese-containing material is at least one of manganese acetate, manganese carbonate, manganese oxalate and manganese oxide.
5. The method according to claim 1, wherein in the step (2), the electrospinning conditions comprise a nozzle hole diameter of 500 to 800 μm, a feeding speed of 0.2 to 0.8m L/h, a voltage of 20 to 40kV, a solidification distance between the nozzle and the collector of 15 to 35cm, and a pressure of 0.3 to 0.5 MPa.
6. The method according to claim 1 or 5, wherein in the step (2), the diameter of the fiber rod-shaped precursor is 20 to 150 nm.
7. The method of claim 1, wherein in step (3), the high temperature annealing conditions: heating from 25 ℃ to 300-400 ℃ at the speed of 1-10 ℃/min, preserving heat for 2-4h, heating to 700-900 ℃ at the speed of 1-10 ℃/min, preserving heat for 10-16h, and cooling to room temperature along with the furnace.
8. The fluorocarbon co-doped lithium nickel cobalt manganese oxide cathode material is characterized by being prepared by the method in claims 1-7.
9. A lithium battery, which is characterized by comprising the fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material as defined in claim 8.
10. An energy storage device, characterized in that the energy storage device has the lithium battery of claim 9.
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