CN108767251B - Layered porous cubic micro-nano structure lithium ion battery anode material - Google Patents

Layered porous cubic micro-nano structure lithium ion battery anode material Download PDF

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CN108767251B
CN108767251B CN201810670029.9A CN201810670029A CN108767251B CN 108767251 B CN108767251 B CN 108767251B CN 201810670029 A CN201810670029 A CN 201810670029A CN 108767251 B CN108767251 B CN 108767251B
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lithium ion
ion battery
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layered porous
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CN108767251A (en
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张永兴
李佳
霍旺
徐倩倩
李丽
王飞
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Huaibei Normal 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
    • 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

Abstract

The invention disclosesA layered porous cubic micro-nano structure lithium ion battery cathode material is prepared by mixing a precipitator, a copper source, a cobalt source, a solvent and a surfactant, and annealing the mixture by a mixed solvothermal method and a precursor to prepare CuCo with a monodisperse layered porous cubic micro-nano structure2O4The material is used for the cathode material of the lithium ion battery. According to the invention, a monodisperse layered porous cubic micro-nano structure assembled by nano particles is constructed by skillfully regulating the volume ratio of glycerol to water, the dosage of a surfactant and the heat treatment conditions, so that the structure has excellent electrochemical performance; the first discharge capacity is high, and the cycle stability is excellent; the reaction reagent is convenient and easy to obtain, and is green and environment-friendly; high yield and purity, large specific surface area of the obtained material, good size uniformity and suitability for large-scale production.

Description

Layered porous cubic micro-nano structure lithium ion battery anode material
Technical Field
The invention relates to a lithium ion battery cathode material, in particular to a layered porous cubic micro-nano structure lithium ion battery cathode material.
Background
The micro-nano structure is composed of secondary nano structure units, so that the diffusion path of lithium ions can be effectively shortened, the obstruction of the lithium ions in diffusion is reduced, and the lithium ions and electrolyte can easily enter the electrode material; the existence of the secondary nanostructure unit can increase the specific surface area of the electrode material, so that the electrolyte can be more fully contacted with the active material, and active sites capable of reacting with lithium ions are increased; after the secondary nano structure units are assembled to form a micro-nano structure, some porous structures generally exist, so that the secondary nano structure units not only can be used as a buffer area of lithium ions, but also can store certain electrolyte, and more importantly, can buffer volume expansion in the charging and discharging process.
CuCo2O4Is an AB with a spinel structure2O4Of a bimetallic transition metal oxide ofIn the structure, copper ions occupy octahedral sites, and cobalt ions occupy both octahedral and tetrahedral sites. Compared with single copper oxide and single cupric oxide, copper cobaltate has higher conductivity and electrochemical activity and higher theoretical capacity, is considered as an electrode material with research prospect and is used for solving the problems of energy and environment. Therefore, in the prior art, micro-nano copper cobaltates with different morphologies, such as nanowire arrays, hollow spheres, porous microspheres, nanosheets and the like, are researched and prepared, and are widely used for lithium ion negative electrode materials. And the existing preparation process is many, but the reaction condition is simple, the structure is controllable, and CuCo with a monodisperse layered porous cubic micro-nano structure can be effectively prepared2O4The processes of (A) are rarely reported, and need to be studied deeply.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a monodisperse layered porous cubic micro-nano CuCo structure assembled by nano particles2O4The lithium ion battery cathode material and the preparation method thereof are disclosed, a mixed solvent thermal method which is simple and easy to operate is adopted, the preparation process is simple, the cost is lower, the environment is protected, the obtained product has uniform particles, good appearance, small agglomeration degree and excellent performance, industrialization can be easily realized, and the requirements of people on the lithium ion battery cathode material can be met.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a lithium ion battery cathode material with a layered porous cubic micro-nano structure is prepared by mixing a precipitator, a copper source, a cobalt source, a solvent and a surfactant, and annealing the mixture by a mixed solvothermal method and a precursor to prepare CuCo with a monodisperse layered porous cubic micro-nano structure2O4The material is used for the cathode material of the lithium ion battery.
Further, the precipitator is urea, the tetrahydrate copper acetate is a copper source, the tetrahydrate cobalt acetate is a cobalt source, the glycerol and the deionized water are used as solvents, and the hexadecyl trimethyl ammonium bromide is a surfactant.
Further, the preparation method comprises the following specific steps:
firstly, accurately weighing a certain weight part of copper acetate tetrahydrate, cobalt acetate tetrahydrate, urea and hexadecyl trimethyl ammonium bromide, adding glycerol and deionized water in a certain volume ratio, and preparing a clear mixed solution under the stirring action;
secondly, transferring the clear solution uniformly mixed in the step one into a hydrothermal reaction kettle, setting corresponding temperature, and heating at constant temperature until the reaction is complete;
thirdly, after the reaction is completed, cooling and precipitating, centrifugally washing the precipitate by deionized water and absolute ethyl alcohol, performing solid-liquid separation to obtain pink solid, and drying the pink solid in a vacuum drying oven to obtain pink solid powder;
fourthly, annealing the product obtained in the third step in an air environment at a certain temperature, and cooling to room temperature to obtain a black finished product.
Further, in the first step, 2-6 parts by weight of copper acetate tetrahydrate, 4-12 parts by weight of cobalt acetate tetrahydrate, 16-48 parts by weight of urea, 0.2-0.5 part by weight of hexadecyl trimethyl ammonium bromide, and the volume ratio of glycerol to deionized water is 120: 30-90: 90, the mass ratio of the volume of the glycerol to the volume of the copper acetate tetrahydrate is 60-15: 1, and the mass ratio of the volume of the deionized water to the volume of the copper acetate tetrahydrate is 15-45: 1.
Further, in the second step, polytetrafluoroethylene is lined in the hydrothermal reaction kettle, the temperature is set to be 110-170 ℃, and the heating time is 8-12 hours.
Further, in the third step, the cooling and precipitating time is 10-12 h, and the deionized water and the absolute ethyl alcohol are respectively washed for 3 times in a centrifugal mode.
Further, in the third step, the temperature of the vacuum drying oven is set to be 40-70 ℃.
Further, in the fourth step, annealing is carried out in an air environment, the dried raw materials are placed into a resistance furnace, the heating rate is 1-4 ℃/min, the temperature is increased to 300-600 ℃, and the temperature is maintained for 2-6 hours.
The invention has the beneficial effects that:
1. the monodisperse layered porous cubic micro-nano junction assembled by nano particles is constructed by skillfully regulating the volume ratio of glycerol to water, the dosage of a surfactant and the heat treatment conditionsStructure of CuCo2O4The lithium ion battery cathode material has the porous characteristic and the layered cubic structure, is very beneficial to the permeation of electrolyte ions, can greatly increase the specific surface area of the material, has great promotion effect on the increase of active sites participating in electrochemical reaction, and has excellent electrochemical performance;
2. the discharge capacity is still 1338.6 mAh/g after 300 times of circulation under the current density of 0.5A/g, the charge-discharge efficiency is almost 100 percent, and the excellent circulation stability performance is realized;
3. the reaction reagent required in the preparation process is convenient and easy to obtain, does not generate harmful substances, and is green and environment-friendly; the method has the advantages of flexible and simple operation, mild reaction conditions, high yield, high purity, large specific surface area of the obtained material, good size uniformity, suitability for large-scale production and good application prospect.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 shows a monodisperse layered porous cubic micro-nano CuCo structure assembled by nanoparticles2O4An X-ray diffraction pattern (XRD) pattern of the lithium ion battery negative electrode material;
FIG. 2 shows a monodisperse layered porous cubic micro-nano CuCo structure assembled by nanoparticles2O4Scanning Electron Microscope (SEM) pictures of lithium ion battery cathode materials;
FIG. 3 shows a monodisperse layered porous cubic micro-nano CuCo structure assembled by nanoparticles2O4High power Scanning Electron Microscope (SEM) photographs of the lithium ion battery negative electrode material;
FIG. 4 shows that the monodisperse layered porous cubic micro-nano CuCo structure is assembled by nano particles2O4A low-power Transmission Electron Microscope (TEM) photograph of the lithium ion battery negative electrode material;
FIG. 5 shows a monodisperse layered porous cubic micro-nano CuCo structure assembled by nanoparticles2O4High-power Transmission Electron Microscope (TEM) photograph of lithium ion battery negative electrode material；
FIG. 6 shows a monodisperse layered porous cubic micro-nano CuCo structure assembled by nanoparticles2O4A rate performance graph of the lithium ion battery cathode material;
FIG. 7 shows a monodisperse layered porous cubic micro-nano CuCo structure assembled by nanoparticles2O4And (3) a cycle performance diagram of the lithium ion battery negative electrode material.
Detailed Description
Example 1
(1) Weighing 0.2g of copper acetate tetrahydrate, 0.4g of cobalt acetate tetrahydrate, 0.45g of hexadecyltrimethylammonium bromide and 1.2g of urea, putting the weighed materials into a clean beaker, adding 30ml of a mixed solution of glycerol and deionized water (the volume ratio of the mixed solution of glycerol and deionized water is 3: 1), and fully stirring the mixture to obtain a uniform and clear solution;
(2) transferring the uniformly mixed clear solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene inner container, sealing completely, heating at the constant temperature of 130 ℃ for 9 hours, taking out the inner container, pouring out the upper-layer waste liquid, adding water, transferring into a centrifuge tube with a specified model for centrifugal separation, and respectively washing with deionized water and absolute ethyl alcohol for three times;
(3) putting the pink sample obtained in the step (2) into a drying box, adjusting the temperature to 60 ℃, and drying to obtain pink solid powder;
(4) and (4) putting the pink solid obtained in the step (3) into a completely dried quartz boat, placing the quartz boat into a resistance furnace with controllable heating rate, heating the resistance furnace at the speed of 1-4 ℃/min in an air environment, maintaining the temperature at 350 ℃ for 4 hours, and cooling the temperature to room temperature to obtain a black finished product.
The obtained CuCo is shown in FIG. 12O4An XRD (X-ray diffraction) spectrum of the product is measured by an XRD instrument; as can be seen from FIG. 1, the product produced has CuCo2O4Spinel phase structure;
as shown in FIG. 2, the obtained CuCo2O4Scanning Electron Microscope (SEM) pictures of the product obtained by SEM; as can be seen from FIG. 2, the CuCo2O4The structure is a monodisperse laminar cubic structure, and the sizes of the cubic structure are not greatly different and are between about 600 and 800 nm;
as shown in FIG. 3, the resulting CuCo2O4Scanning Electron Microscope (SEM) pictures of the product obtained by the SEM; as can be seen from FIG. 3, the monodisperse cubic CuCo2O4The microstructure is assembled by nano particles, and the structure has obvious porous characteristic and a layered structure;
as shown in FIG. 4, the resulting CuCo2O4A low-power Transmission Electron Microscope (TEM) picture of the product is obtained through a TEM; as can be seen from FIG. 4, the monodisperse cubic CuCo was further confirmed2O4Is assembled by nano particles, and the structure has the characteristics of a porous structure and a layered structure;
as shown in FIG. 5, the obtained CuCo2O4A high-power Transmission Electron Microscope (TEM) picture of the product is obtained by a TEM; as can be seen from FIG. 5, the layered porous cubic structure CuCo2O4Is composed of nanoparticles with an average size of 35 nm;
as shown in FIG. 6, the obtained CuCo2O4The product is used as a rate performance graph of the lithium ion battery cathode; as can be seen from FIG. 6, the discharge capacity at 0.1A/g is 1152mAh/g for the first time, and the discharge capacity at 5A/g is 676 mAh/g for the high current density, which has excellent high rate capability;
as shown in FIG. 7, the resulting CuCo2O4The product is used as a cycle performance diagram of the lithium ion battery cathode; as can be seen from FIG. 7, the discharge capacity was maintained at 1338.6 mAh/g even after 300 cycles at a current density of 0.5A/g, and the charge-discharge efficiency was almost 100%, indicating that the product had excellent stability.
Example 2
(1) Weighing 0.2g of copper acetate tetrahydrate, 0.4g of cobalt acetate tetrahydrate, 0.45g of hexadecyltrimethylammonium bromide and 1.2g of urea, putting the weighed materials into a clean beaker, adding 30ml of a mixed solution of glycerol and deionized water (the volume ratio of the mixed solution of glycerol and deionized water is 2: 1), and fully stirring the mixture to obtain a uniform and clear solution;
(2) transferring the uniformly mixed clear solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene inner container, sealing completely, heating at the constant temperature of 130 ℃ for 9 hours, taking out the inner container, pouring out the upper-layer waste liquid, adding water, transferring into a centrifuge tube with a specified model for centrifugal separation, and respectively washing with deionized water and absolute ethyl alcohol for three times;
(3) putting the pink sample obtained in the step (2) into a drying box, adjusting the temperature to 60 ℃, and drying to obtain pink solid powder;
(4) and (4) putting the pink solid obtained in the step (3) into a completely dried quartz boat, placing the quartz boat into a resistance furnace with controllable heating rate, heating the resistance furnace at the speed of 1-4 ℃/min in an air environment, maintaining the temperature at 400 ℃ for 4 hours, and cooling the temperature to room temperature to obtain a black finished product.
Example 3
(1) Weighing 0.2g of copper acetate tetrahydrate, 0.4g of cobalt acetate tetrahydrate, 0.45g of hexadecyltrimethylammonium bromide and 1.2g of urea, putting the weighed materials into a clean beaker, adding 30ml of a mixed solution of glycerol and deionized water (the volume ratio of the mixed solution of glycerol and deionized water is 1: 1), and fully stirring the mixture to obtain a uniform and clear solution;
(2) transferring the uniformly mixed clear solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene inner container, sealing completely, heating at the constant temperature of 130 ℃ for 9 hours, taking out the inner container, pouring out the upper-layer waste liquid, adding water, transferring into a centrifuge tube with a specified model for centrifugal separation, and respectively washing with deionized water and absolute ethyl alcohol for three times;
(3) putting the pink sample obtained in the step (2) into a drying box, adjusting the temperature to 60 ℃, and drying to obtain pink solid powder;
(4) and (4) putting the pink solid obtained in the step (3) into a completely dried quartz boat, placing the quartz boat into a resistance furnace with controllable heating rate, heating the resistance furnace at the speed of 1-4 ℃/min in an air environment, maintaining the temperature at 350 ℃ for 9 hours, and cooling the temperature to room temperature to obtain a black finished product.
Example 4
(1) Weighing 0.2g of copper acetate tetrahydrate, 0.4g of cobalt acetate tetrahydrate, 0.45g of hexadecyltrimethylammonium bromide and 1.2g of urea, putting the weighed materials into a clean beaker, adding 30ml of a mixed solution of glycerol and deionized water (the volume ratio of the mixed solution of glycerol and deionized water is 4: 1), and fully stirring the mixture to obtain a uniform and clear solution;
(2) transferring the uniformly mixed clear solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene inner container, sealing completely, heating at the constant temperature of 150 ℃ for 9 hours, taking out the inner container, pouring out the upper-layer waste liquid, adding water, transferring into a centrifuge tube with a specified model for centrifugal separation, and respectively washing with deionized water and absolute ethyl alcohol for three times;
(3) putting the pink sample obtained in the step (2) into a drying box, adjusting the temperature to 60 ℃, and drying to obtain pink solid powder;
(4) and (4) putting the pink solid obtained in the step (3) into a completely dried quartz boat, placing the quartz boat into a resistance furnace with controllable heating rate, heating the resistance furnace at the speed of 1-4 ℃/min in an air environment, maintaining the temperature at 300 ℃ for 9 hours, and cooling the temperature to room temperature to obtain a black finished product.
Example 5
(1) Weighing 0.2g of copper acetate tetrahydrate, 0.4g of cobalt acetate tetrahydrate, 0.45g of hexadecyltrimethylammonium bromide and 1.2g of urea, putting the weighed materials into a clean beaker, adding 30ml of a mixed solution of glycerol and deionized water (the volume ratio of the mixed solution of glycerol and deionized water is 4: 1), and fully stirring the mixture to obtain a uniform and clear solution;
(2) transferring the uniformly mixed clear solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene inner container, sealing completely, heating at the constant temperature of 170 ℃ for 9 hours, taking out the inner container, pouring out the upper-layer waste liquid, adding water, transferring into a centrifugal tube with a specified model for centrifugal separation, and respectively washing with deionized water and absolute ethyl alcohol for three times;
(3) putting the pink sample obtained in the step (2) into a drying box, adjusting the temperature to 60 ℃, and drying to obtain pink solid powder;
(4) and (4) putting the pink solid obtained in the step (3) into a completely dried quartz boat, placing the quartz boat into a resistance furnace with controllable heating rate, heating the resistance furnace at the speed of 1-4 ℃/min in an air environment, maintaining the temperature at 450 ℃ for 4 hours, and cooling the temperature to room temperature to obtain a black finished product.
Example 6
(1) Weighing 0.2g of copper acetate tetrahydrate, 0.4g of cobalt acetate tetrahydrate, 0.45g of hexadecyltrimethylammonium bromide and 0.8g of urea, putting the materials into a clean beaker, adding 30ml of mixed solution of glycerol and deionized water (the volume ratio of the mixed solution of glycerol and deionized water is 2: 1), and fully stirring to obtain uniform clear solution
(2) Transferring the uniformly mixed clear solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene inner container, sealing completely, heating at the constant temperature of 130 ℃ for 9 hours, taking out the inner container, pouring out the upper-layer waste liquid, adding water, transferring into a centrifuge tube with a specified model for centrifugal separation, and respectively washing with deionized water and absolute ethyl alcohol for three times;
(3) putting the pink sample obtained in the step (2) into a drying box, adjusting the temperature to 80 ℃, and drying to obtain pink solid powder;
(4) and (4) putting the pink solid obtained in the step (3) into a completely dried quartz boat, placing the quartz boat into a resistance furnace with controllable heating rate, heating the resistance furnace at the speed of 1-4 ℃/min in an air environment, maintaining the temperature at 450 ℃ for 4 hours, and cooling the temperature to room temperature to obtain a black finished product.
Example 7
(1) Weighing 0.2g of copper acetate tetrahydrate, 0.4g of cobalt acetate tetrahydrate, 0.45g of hexadecyltrimethylammonium bromide and 1.5g of urea, putting the weighed materials into a clean beaker, adding 30ml of a mixed solution of glycerol and deionized water (the volume ratio of the mixed solution of glycerol and deionized water is 2: 1), and fully stirring the mixture to obtain a uniform and clear solution;
(2) transferring the uniformly mixed clear solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene inner container, sealing completely, heating at the constant temperature of 150 ℃ for 10 hours, taking out the inner container, pouring out upper-layer waste liquid, adding water, transferring into a centrifugal tube of a specified model for centrifugal separation, and respectively washing with deionized water and absolute ethyl alcohol for three times;
(3) putting the pink sample obtained in the step (2) into a drying box, adjusting the temperature to 60 ℃, and drying to obtain pink solid powder;
(4) and (4) putting the pink solid obtained in the step (3) into a completely dried quartz boat, placing the quartz boat into a resistance furnace with controllable heating rate, heating the resistance furnace at the speed of 1-4 ℃/min in an air environment, maintaining the temperature at 350 ℃ for 9 hours, and cooling the temperature to room temperature to obtain a black finished product.
Example 8
(1) Weighing 0.2g of copper acetate tetrahydrate, 0.4g of cobalt acetate tetrahydrate, 0.45g of hexadecyl trimethyl ammonium bromide and 1.2g of urea, putting into a clean beaker, adding 30ml of a mixed solution of glycerol and deionized water (the volume ratio of the mixed solution of ethylene glycol and deionized water is 1: 1), and then fully stirring to obtain a uniform and clear solution;
(2) transferring the uniformly mixed clear solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene inner container, sealing completely, heating at the constant temperature of 130 ℃ for 11 hours, taking out the inner container, pouring out the upper-layer waste liquid, adding water, transferring into a centrifuge tube with a specified model for centrifugal separation, and respectively washing with deionized water and absolute ethyl alcohol for three times;
(3) putting the pink sample obtained in the step (2) into a drying box, adjusting the temperature to 60 ℃, and drying to obtain pink solid powder;
(4) and (3) putting the pink solid obtained in the step (3) into a completely dried quartz boat, placing the quartz boat into a resistance furnace with controllable heating rate, heating the resistance furnace at the rate of 1-4 ℃/min in an air environment, maintaining the temperature at 450 ℃ for 3 hours, and cooling the temperature to room temperature to obtain a black finished product.
Example 9
(1) Weighing 0.2g of copper acetate tetrahydrate, 0.4g of cobalt acetate tetrahydrate, 0.45g of hexadecyl trimethyl ammonium bromide and 1.2g of urea, putting into a clean beaker, adding 30ml of a mixed solution of glycerol and deionized water (the volume ratio of the mixed solution of ethylene glycol and deionized water is 1: 1), and then fully stirring to obtain a uniform and clear solution;
(2) transferring the uniformly mixed clear solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene inner container, completely sealing, heating at the constant temperature of 170 ℃ for 12 hours, taking out the inner container, pouring out the upper-layer waste liquid, adding water, transferring into a centrifugal tube of a specified model for centrifugal separation, and respectively washing with deionized water and absolute ethyl alcohol for three times;
(3) putting the pink sample obtained in the step (2) into a drying box, adjusting the temperature to 60 ℃, and drying to obtain pink solid powder;
(4) and (4) putting the pink solid obtained in the step (3) into a completely dried quartz boat, placing the quartz boat into a resistance furnace with controllable heating rate, heating the resistance furnace at the speed of 1-4 ℃/min in an air environment, maintaining the temperature at 350 ℃ for 4 hours, and cooling the temperature to room temperature to obtain a black finished product.
Example 10
(1) Weighing 0.2g of copper acetate tetrahydrate, 0.4g of cobalt acetate tetrahydrate, 0.45g of hexadecyl trimethyl ammonium bromide and 1.2g of urea, putting into a clean beaker, adding 30ml of a mixed solution of glycerol and deionized water (the volume ratio of the mixed solution of ethylene glycol and deionized water is 1: 1), and then fully stirring to obtain a uniform and clear solution;
(2) transferring the uniformly mixed clear solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene inner container, sealing completely, heating at the constant temperature of 170 ℃ for 10 hours, taking out the inner container, pouring out the upper-layer waste liquid, adding water, transferring into a centrifugal tube of a specified model for centrifugal separation, and respectively washing with deionized water and absolute ethyl alcohol for three times;
(3) putting the pink sample obtained in the step (2) into a drying box, adjusting the temperature to 60 ℃, and drying to obtain pink solid powder;
(4) and (4) putting the pink solid obtained in the step (3) into a completely dried quartz boat, placing the quartz boat into a resistance furnace with controllable heating rate, heating the resistance furnace at the speed of 1-4 ℃/min in an air environment, maintaining the temperature at 350 ℃ for 4 hours, and cooling the temperature to room temperature to obtain a black finished product.
The technical effects to be achieved by the present application can be achieved by verifying the products obtained in examples 2 to 10, which explains that the volume ratio of glycerin to water, the amount of the surfactant and the heat treatment conditions are skillfully regulated to constructCuCo with layered porous cubic micro-nano structure assembled by nano particles2O4The porous characteristic and the layered structure of the lithium ion battery cathode material are very beneficial to the permeation of electrolyte ions, and meanwhile, the specific surface area of the material can be greatly increased, so that the lithium ion battery cathode material has a great promotion effect on the increase of active sites participating in electrochemical reaction, and has excellent electrochemical performance.
The discharge capacity is still 1338.6 mAh/g after 300 times of circulation under the current density of 0.5A/g, the charge-discharge efficiency is almost 100 percent, and the excellent circulation stability performance is realized;
the reaction reagent required in the preparation process is convenient and easy to obtain, does not generate harmful substances, and is green and environment-friendly; the method has the advantages of flexible and simple operation, mild reaction conditions, high yield, high purity, large specific surface area of the obtained material, good size uniformity, suitability for large-scale production and good application prospect.
The embodiments of the present invention disclosed herein are only for explaining the technical solutions of the present invention, and are not to be taken as limiting the contents of the present invention. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by those skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (5)

1. The layered porous cubic micro-nano structure lithium ion battery cathode material is characterized in that: mixing a precipitator, a copper source, a cobalt source, a solvent and a surfactant, and annealing by a mixed solvothermal method and a precursor to prepare CuCo with a monodisperse layered porous cubic micro-nano structure2O4The material is used for the cathode material of the lithium ion battery; the precipitator is urea, copper acetate tetrahydrate is a copper source, cobalt acetate tetrahydrate is a cobalt source, glycerol and deionized water are used as solvents, and hexadecyl trimethyl ammonium bromide is a surfactant; the preparation method comprises the following specific steps:
firstly, accurately weighing a certain weight part of copper acetate tetrahydrate, cobalt acetate tetrahydrate, urea and hexadecyl trimethyl ammonium bromide, adding glycerol and deionized water in a certain volume ratio, and preparing a clear mixed solution under the stirring action;
secondly, transferring the clear solution uniformly mixed in the step one into a hydrothermal reaction kettle, setting corresponding temperature, and heating at constant temperature until the reaction is complete;
thirdly, after the reaction is completed, cooling and precipitating, centrifugally washing the precipitate by deionized water and absolute ethyl alcohol, performing solid-liquid separation to obtain pink solid, and drying the pink solid in a vacuum drying oven to obtain pink solid powder;
fourthly, annealing the product obtained in the third step in an air environment at a certain temperature, and cooling to room temperature to obtain a black finished product;
in the first step, 2-6 parts by weight of copper acetate tetrahydrate, 4-12 parts by weight of cobalt acetate tetrahydrate, 16-48 parts by weight of urea, 0.2-0.5 part by weight of hexadecyl trimethyl ammonium bromide, and the volume ratio of glycerol to deionized water is 120: 30-90: 90.
2. the layered porous cubic micro-nano structure lithium ion battery anode material according to claim 1, which is characterized in that: in the second step, polytetrafluoroethylene is lined in the hydrothermal reaction kettle, the temperature is set to be 110-170 ℃, and the heating time is 8-12 hours.
3. The layered porous cubic micro-nano structure lithium ion battery anode material according to claim 1, which is characterized in that: and in the third step, the cooling and precipitating time is 10-12 h, and the deionized water and the absolute ethyl alcohol are respectively used for centrifugal washing for 3 times.
4. The layered porous cubic micro-nano structure lithium ion battery anode material according to claim 1, which is characterized in that: in the third step, the temperature of the vacuum drying oven is set to be 40-70 ℃.
5. The layered porous cubic micro-nano structure lithium ion battery anode material according to claim 1, which is characterized in that: in the fourth step, annealing is carried out in an air environment, the dried raw materials are placed into a resistance furnace, the heating rate is 1-4 ℃/min, the temperature is increased to 300-600 ℃, and the temperature is maintained for 2-6 hours.
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