CN113066966A - Multi-layer core-shell structure binary cobalt-nickel metal oxide coated polyaniline nanocomposite material and preparation method and application thereof - Google Patents
Multi-layer core-shell structure binary cobalt-nickel metal oxide coated polyaniline nanocomposite material and preparation method and application thereof Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention provides a multilayer core-shell structure binary cobalt-nickel metal oxide coated polyaniline nano composite material and a preparation method and application thereof, wherein a self-template, cobalt salt and nickel salt are used as raw materials, and a hydrothermal reaction is carried out in high-purity water to synthesize a binary cobalt-nickel metal oxide carbon microsphere precursor; then, the carbon in the microspheres is removed by high-temperature calcination in an air atmosphere through a muffle furnace, and in the high-temperature annealing process, three-layer core-shell Co with unique morphology is formed under the influence of shrinkage force and adhesion force3O4NiO hollow microspheres and in-situ growing polyaniline nanoneedles on the surfaces of the microspheres. The hollow core-shell structure is favorable for electronic transmission, and the flexible polyaniline nanoneedle wrapped on the outer surface of the ball body solves the problem that the hollow ball body is subjected to multiple charge-discharge cyclesThe medium structure is easy to break and collapse to cause the deterioration of the cycle performance, and the material applied to the lithium ion battery has the advantages of good cycle performance, high specific energy density and the like.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a multi-layer core-shell structure binary cobalt-nickel metal oxide coated polyaniline nanocomposite material, and a preparation method and application thereof, which are used for manufacturing a lithium ion battery cathode.
Background
Since fossil fuels are limited and combustion causes a series of environmental problems, clean energy sources such as solar energy, hydraulic energy, nuclear energy and the like have not been developed as alternative energy sources.
Lithium ion batteries, as a chemical energy storage device, have been widely used in the fields of portable electronic devices, electric vehicles, energy storage, and the like, due to their advantages of high energy density, high output voltage, excellent cycle performance, and the like. At present, the commercial lithium ion battery cathode material is mainly a graphite carbon material, the theoretical capacity of the graphite carbon material is low, and the improvement of the electrochemical performance of the lithium ion battery is limited, so that the design and preparation of the high-performance lithium ion battery cathode material are the key points for meeting the performance enhancement and the application expansion of the lithium ion battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides a binary cobalt nickel metal oxide coated polyaniline nanocomposite material with a multilayer core-shell structure and a preparation method thereof. The preparation method is simple, the cost is low, and the yield is high.
The invention also aims to provide application of the binary cobalt nickel metal oxide coated polyaniline nanocomposite with the multilayer core-shell structure to a negative electrode of a lithium ion battery.
The technical scheme adopted by the invention is as follows:
a preparation method of a multilayer core-shell structure binary cobalt nickel metal oxide coated polyaniline nanocomposite material comprises the following steps:
1) dissolving a self-template, cobalt salt and nickel salt in water, and carrying out hydrothermal reaction to obtain a binary cobalt-nickel metal oxide carbon microsphere precursor;
2) calcining the binary cobalt nickel metal oxide carbon microsphere precursor obtained in the step 1) at a high temperature in air, and cooling to room temperature to obtain a multilayer core-shell structure binary cobalt nickel oxide microsphere;
3) and (3) coating polyaniline on the multilayer core-shell structure binary cobalt nickel oxide microspheres obtained in the step 2) in an ice bath to obtain the multilayer core-shell structure binary cobalt nickel metal oxide coated polyaniline nanocomposite.
The water in the step 1) is high-purity water; so as to avoid other impurities from influencing the experimental result.
The template in the step 1) is glucose or sucrose, and mainly plays a role of a self template in hydrothermal reaction, the glucose or the sucrose is subjected to glycidyl polymerization at high temperature to form carbon spheres, and simultaneously, metal cations are adsorbed to permeate into the carbon spheres for in-situ coordination;
the diameter of the binary cobalt nickel metal oxide carbon microsphere precursor obtained in the step 1) is 2-5 μm.
Further, in the step 1), the ratio of the amounts of the self-template, cobalt salt and nickel salt is 14: 10: 5; and controlling according to the dosage ratio to obtain the uniform and stable microspheres and obtain the multilayer core-shell structure.
Preferably, the cobalt salt is cobalt acetate tetrahydrate; the nickel salt is nickel acetate tetrahydrate; the multilayer core-shell structure formed by the two salts has more layers, is not easy to break and has stable performance. The concentration of the cobalt salt in water is 0.1-0.4M.
In the step 1), the hydrothermal reaction is carried out under the condition of 150-180 ℃ for 0.5-8 hours;
preferably, the reaction temperature is 180 ℃ and the reaction time is 8 hours.
In the step 1), after the reaction is finished, centrifuging, washing and drying are carried out.
In the step 2), the high-temperature calcination specifically comprises the following steps: placing the binary cobalt-nickel metal oxide carbon microsphere precursor in a porcelain boat, placing the porcelain boat in a muffle furnace, and calcining in an air atmosphere to remove a carbon sphere template;
further, the high-temperature calcination condition is calcination at 500-600 ℃ for 1-3 hours; and (2) removing the carbon sphere template from the binary cobalt nickel metal oxide carbon microspheres obtained in the step (1) at the calcination temperature, and further obtaining the binary cobalt nickel metal oxide microspheres with a multilayer core-shell structure. The calcination temperature is preferably 600 ℃ and the calcination time is preferably 2 hours.
During high-temperature calcination, the carbon template in the binary cobalt-nickel metal oxide carbon microsphere precursor is oxidized and removed, the sphere shrinks in the annealing process, and the metal oxide crystal continuously forms a shell layer due to the difference of the adhesion force and the shrinkage force in the radial direction of the sphere.
The step 3) comprises the following specific steps:
3-1) ultrasonically dispersing the binary cobalt nickel metal oxide microspheres with the multilayer core-shell structure obtained in the step 2) in a dilute acid solution, and adding aniline into the dilute acid solution to obtain a solution a;
3-2) dissolving an initiator in a dilute acid solution to obtain a solution b; and (4) dropwise adding the solution b into the solution a, and stirring in an ice bath for reaction.
In step 3), the ratio of the amounts of aniline and initiator is 2: 1.
the concentration range of the dilute acid solution in the step 3-1) is 0.2-0.5M;
in the step 3-1), the ratio of the using amount of the binary cobalt nickel metal oxide microspheres with the multilayer core-shell structure to the using amount of the aniline is 0.1-0.3: 110-460 g/. mu.L;
in the step 3-1), the ratio of the usage of the binary cobalt nickel metal oxide microspheres of the multilayer core-shell structure to the usage of the dilute sulfuric acid solution is 0.1-0.3: 50-70 g/mL.
The concentration range of the dilute acid solution in the step 3-2) is 0.2-0.5M;
in the step 3-2), the ammonium persulfate is dissolved in the acid solution, and the concentration is 0.015-0.07mol/L
And 3-2) stirring in an ice bath for reaction, wherein the reaction temperature is 0-2 ℃, the reaction time is 2-12 hours, and the preferable reaction time is 3 hours.
The initiator in the step 3-2) is ammonium persulfate.
The dilute acid solution in the step 3-1) and the step 3-2) is a dilute sulfuric acid solution or a dilute hydrochloric acid solution, and preferably a dilute sulfuric acid solution.
In the step 3-2), after the reaction is finished, centrifuging, washing and drying a product; the drying condition is drying for 10-12 hours in an oven at 60-80 ℃.
And 3) mainly using a chemical oxidation method to grow conductive polymer polyaniline on the surface of the multilayer core-shell structure binary cobalt-nickel metal oxide microsphere obtained in the step 2) in situ. The method is mainly characterized in that a water-soluble initiator is adopted to initiate monomer aniline to generate oxidative polymerization in an acid medium. The conductivity and morphology of the synthesized polyaniline are mainly influenced by the type and concentration of acid in a reaction medium, the type and concentration of an initiator, the concentration of an aniline monomer, the reaction temperature, the reaction time and the like. The initiator mainly comprises ammonium persulfate, and the ammonium persulfate does not contain metal ions, has strong oxidizing ability and convenient post-treatment and is the most common initiator. The preferred acid for this experiment was dilute sulfuric acid and the initiator was ammonium persulfate.
The invention provides a binary cobalt-nickel metal oxide coated polyaniline nanocomposite with a multilayer core-shell structure, which is prepared by adopting the method. The size of the obtained multilayer core-shell structure binary cobalt nickel metal oxide coated polyaniline nano composite material is 2-5 mu m micron spheres, and the specific morphology is shown in figure 4.
The invention provides an application of a binary cobalt nickel metal oxide coated polyaniline nanocomposite with a multilayer core-shell structure, which is used for a lithium ion battery.
Specifically, the multi-layer core-shell structure binary cobalt nickel metal oxide coated polyaniline nanocomposite is used as an active material to prepare the lithium ion battery cathode, so that the lithium ion battery is prepared, and has good cycle performance.
The application method comprises the following steps:
A. coating a polyaniline nano composite material wrapped by a binary cobalt-nickel metal oxide with a multilayer core-shell structure as a negative electrode active material of a lithium battery, uniformly mixing the polyaniline nano composite material with a mixture of conductive carbon black, CMC and SBR in a ratio of 7:2:1 or 8:1:1, magnetically stirring for 8-12 hours, coating the prepared slurry on a copper foil by using a coater, placing the copper foil in a vacuum drying oven at the temperature of 60-80 ℃, drying for 8-12 hours, taking out, and cutting the copper foil into a small circular electrode plate by using a cutting machine;
B. the prepared electrode slice is assembled into a button battery in a glove box which is filled with high-purity argon and has the water oxygen value of less than or equal to 0.01ppm, and the electrolyte is a solution which takes Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) as solvents in the volume ratio of 1:1:1 and 1M LiPF6 as solute.
The specific method for assembling the battery comprises the following steps: the electrode plate is placed after one drop of electrolyte is dripped on the electrode shell, then the diaphragm is placed after 1 drop of electrolyte is dripped on the electrode shell, the lithium sheet is placed on the diaphragm to serve as a counter electrode, then the gasket and the elastic sheet are respectively placed, the battery is compressed and sealed by a hydraulic press, and the battery is placed for 6-8 hours.
According to the preparation method of the multilayer core-shell structure binary cobalt-nickel metal oxide coated polyaniline nano composite material, a self-template, cobalt salt and nickel salt are used as raw materials, and a hydrothermal reaction is performed in high-purity water to synthesize a binary cobalt-nickel metal oxide carbon microsphere precursor; then, the carbon in the microspheres is removed by high-temperature calcination in an air atmosphere through a muffle furnace, and in the high-temperature annealing process, three-layer core-shell Co with unique morphology is formed under the influence of shrinkage force and adhesion force3O4NiO hollow microspheres, and then growing polyaniline nanoneedles on the surfaces of the hollow microspheres in situ. The hollow core-shell structure is beneficial to electron transmission, the internal cavity of the three-layer core-shell structure has larger volume and more reactive sites, and is more beneficial to ion transmission. Meanwhile, the flexible polyaniline nanoneedle wrapped on the outer surface of the sphere overcomes the defect that the structure of the hollow sphere is easy to break and collapse in multiple charging and discharging cycles, so that the cycle performance is poor.
Compared with the prior art, the invention has the following advantages:
1) the pore channel on the surface of the core-shell structure is beneficial to the electrolyte to better enter the shell layer, and is beneficial to electron transmission;
2) the volume of the internal cavity can relieve the volume expansion caused in the charging and discharging process;
3) the needle-punched polyaniline wrapped on the surface of the sphere improves the conductivity of the metal oxide, effectively improves the mechanical property of the core-shell oxide micron sphere, and prevents the shell from structural collapse in multiple charge-discharge cycles, thereby optimizing the cycle performance of the material.
4) The raw materials are low in price, the synthesis process is simple, and batch production can be carried out.
Drawings
FIG. 1 is an SEM image of multi-layer core-shell structure binary cobalt nickel metal oxide microspheres prepared in example 1;
FIG. 2 is a TEM image of multi-layer core-shell structure binary cobalt nickel metal oxide microspheres prepared in example 1;
FIG. 3 is an XRD pattern of the multi-layer core-shell structure binary cobalt nickel metal oxide microspheres prepared in example 1;
FIG. 4 is an SEM image of a multi-layer core-shell structure binary cobalt nickel metal oxide coated polyaniline nanocomposite prepared in example 1;
FIG. 5 is a TEM image of the multi-layer core-shell structure binary cobalt-nickel metal oxide-coated polyaniline nanocomposite prepared in example 1;
FIG. 6 is a mapping diagram of the multilayer core-shell structure binary cobalt-nickel metal oxide coated polyaniline nanocomposite prepared in example 1;
FIG. 7 is an XPS plot of a multi-layer core-shell binary cobalt nickel metal oxide coated polyaniline nanocomposite prepared in example 1;
FIG. 8 is an SEM image of multi-layer core-shell structure binary cobalt nickel metal oxide microspheres prepared in comparative example 1;
FIG. 9 is an SEM image of multi-layer core-shell structure binary cobalt nickel metal oxide microspheres prepared in comparative example 2
FIG. 10 is an SEM image of a polyaniline nanocomposite coated with binary cobalt-nickel metal oxide microspheres with a multi-layer core-shell structure prepared in example 2;
FIG. 11 is an SEM image of a polyaniline nanocomposite coated with binary cobalt-nickel metal oxide microspheres with a multi-layer core-shell structure prepared in example 3;
FIG. 12 shows that the negative electrode material of the lithium ion battery made of the composite material of embodiment 4, in which the multi-layer core-shell structure of the composite material of the binary cobalt-nickel metal oxide microspheres wraps the polyaniline nanocomposite material, is 0.5A g-1A charge-discharge curve at current density;
FIG. 13 is the multilayer core-shell structure of example 4The binary cobalt nickel metal oxide micron sphere coated polyaniline nanometer composite material as the negative electrode material of lithium ion battery is 0.5A g-1Cycling performance curve at current density.
Detailed Description
The invention will be described in detail below with reference to the following examples and the accompanying drawings.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A preparation method of a multilayer core-shell structure binary cobalt nickel metal oxide coated polyaniline nanocomposite material comprises the following steps:
1) preparing a binary cobalt nickel metal oxide micron carbon sphere precursor: weighing 0.014mol of glucose, 0.01mol of cobalt acetate tetrahydrate and 0.005mol of nickel acetate tetrahydrate in a beaker, adding 30mL of high-purity water, stirring for 15 minutes under magnetic stirring to completely dissolve the cobalt acetate tetrahydrate, pouring the obtained reddish brown transparent solution into a 50mL polytetrafluoroethylene reaction kettle inner container, reacting for 8 hours at 180 ℃, centrifuging at 8000 revolutions per minute after the reaction is finished, cleaning for three times by using the high-purity water, and drying for 12 hours at 60 ℃ in an oven to obtain a multi-shell binary cobalt nickel metal oxide micron carbon sphere precursor, namely the multi-shell Co metal oxide micron carbon sphere precursor with multiple shells3O4-NiO micron carbon sphere precursor as a blackish brown powder;
2) high-temperature calcination: will be described in detail1) The black brown powder prepared in the method is placed in a porcelain boat and placed in a muffle furnace, the temperature is increased at the speed of 2 ℃/min, the black powder sample is obtained after the reaction is carried out for 2 hours at the temperature of 600 ℃, the temperature is cooled to the room temperature, the SEM and TEM images of the black powder sample are shown in figures 1 and 2, the sample is in the shape of a three-layer core-shell sphere, the surface of the sample is provided with a plurality of micropores, the XRD image is shown in figure 3, and the product obtained in the step is binary cobalt nickel metal oxide Co3O4NiO, the carbon sphere template having been completely oxidatively removed at 600 ℃.
3) In-situ growth of polyaniline: weighing 0.2g of the black powder obtained in the step 2), ultrasonically dispersing the black powder in 60mL of 0.5M dilute sulfuric acid, and adding 115 mu L of aniline to obtain a solution a; and meanwhile, 0.1436g of ammonium persulfate is dissolved in 40mL of 0.5M dilute sulfuric acid solution to obtain solution b, the solution b is slowly dripped into the solution a, and then the solution b is continuously stirred and reacts for 3 hours at the temperature of 0-2 ℃ in ice bath, so that the in-situ growth of polyaniline can be completed. The sample was then centrifuged and washed three times with high purity water and placed in an oven at 60 ℃ for 12 hours. SEM and TEM images of the sample are shown in FIG. 4 and FIG. 5.
Fig. 6 and 7 are mapping and XPS diagrams of the multilayer core-shell structure binary cobalt nickel metal oxide-coated polyaniline nanocomposite prepared in comparative example 1, respectively, which shows that the material coated on the surface of the multilayer core-shell structure is polyaniline.
Comparative example 1
A preparation method of a multilayer core-shell structure binary cobalt nickel metal oxide coated polyaniline nanocomposite material comprises the following steps:
1) the preparation method of the binary cobalt nickel metal oxide micron carbon sphere precursor is the same as that of the embodiment 1;
2) high-temperature calcination: putting the black brown powder prepared in the step 1) into a porcelain boat, putting the porcelain boat into a muffle furnace, reacting for 2 hours at 400 ℃, and raising the temperature at a speed of 2 ℃/min to prepare a black powdery sample, wherein an SEM picture of the sample is shown in figure 8, the sample can be seen to be spherical, but the carbon sphere template is not completely removed due to insufficient reaction temperature.
3) The method for in situ growth of polyaniline is the same as in example 1.
Comparative example 2
A preparation method of a multilayer core-shell structure binary cobalt nickel metal oxide coated polyaniline nanocomposite material comprises the following steps:
1) preparing a binary cobalt nickel metal oxide micron carbon sphere precursor: weighing 0.014mol of glucose, 0.002mol of cobalt acetate tetrahydrate and 0.002mol of nickel acetate tetrahydrate in a beaker, adding 30mL of high purity water, stirring for 15 minutes under magnetic stirring to completely dissolve the cobalt acetate tetrahydrate, pouring the obtained reddish brown transparent solution into a 50mL of polytetrafluoroethylene reaction kettle inner container, reacting for 8 hours at 180 ℃, centrifuging at 8000 revolutions per minute after the reaction is finished, cleaning for three times by using the high purity water, and drying for 12 hours at 60 ℃ in an oven to obtain a multi-shell binary cobalt nickel metal oxide micron carbon sphere precursor;
2) high-temperature calcination: putting the black brown powder prepared in the step 1) into a porcelain boat, putting the porcelain boat into a muffle furnace, reacting for 2 hours at 600 ℃, and heating at a speed of 2 ℃/min to prepare a black powdery sample, wherein an SEM image of the sample is shown in FIG. 9. As can be seen from the figure, when the contents of cobalt acetate and nickel acetate are small, the shell of the oxide microspheres is not easily formed and is easily broken.
Example 2
A preparation method of a multilayer core-shell structure binary cobalt nickel metal oxide coated polyaniline nanocomposite material comprises the following steps:
1) the preparation method of the binary cobalt nickel metal oxide micron carbon spheres is the same as that of the embodiment 1;
2) high temperature calcination was the same as in example 1;
3) in-situ growth of polyaniline: weighing 0.2g of the black powder obtained in the step 2), ultrasonically dispersing the black powder in 60mL of 0.5M dilute sulfuric acid, and adding 455 mu L of aniline into the solution to obtain a solution a; and simultaneously dissolving 0.575g of ammonium persulfate in 40mL of 0.5M dilute sulfuric acid solution to obtain a solution b, slowly dropwise adding the solution b into the solution a, and continuously stirring and reacting for 3 hours at the temperature of 0-2 ℃ in ice bath to complete the in-situ growth of polyaniline. The sample was then centrifuged and washed three times with high purity water and placed in an oven at 60 ℃ for 12 hours. The SEM image of the sample is shown in fig. 9.
Example 3
A preparation method of a multilayer core-shell structure binary cobalt nickel metal oxide coated polyaniline nanocomposite material comprises the following steps:
1) the preparation method of the binary cobalt nickel metal oxide micron carbon spheres is the same as that of the embodiment 1;
2) high temperature calcination was the same as in example 1;
3) in-situ growth of polyaniline: weighing 0.2g of the black powder obtained in the step 2), ultrasonically dispersing the black powder in 60mL of 0.5M dilute sulfuric acid, and adding 228 mu L of aniline to obtain a solution a; and simultaneously dissolving 0.288g of ammonium persulfate in 40mL of 0.5M dilute sulfuric acid solution to obtain a solution b, slowly dropwise adding the solution b into the solution a, and continuously stirring and reacting for 3 hours at the temperature of 0-2 ℃ in ice bath to complete the in-situ growth of polyaniline. The sample was then centrifuged and washed three times with high purity water and placed in an oven at 60 ℃ for 12 hours. The SEM image of the sample is shown in fig. 10.
Example 4
A polyaniline nanocomposite wrapped by binary cobalt-nickel metal oxides with a multilayer core-shell structure is used for medical purposes and is applied to a lithium ion battery, the polyaniline nanocomposite wrapped by the binary cobalt-nickel metal oxides with the multilayer core-shell structure prepared in example 1 is used as a negative electrode active substance of the lithium battery, the polyaniline nanocomposite is uniformly mixed with a mixture of conductive carbon black, CMC and SBR according to the proportion of 7:2:1, magnetic stirring is carried out for 10 hours, prepared slurry is coated on copper foil through a coater, the copper foil is placed in a vacuum drying oven at the temperature of 60 ℃, and after drying is carried out for 2 hours, the copper foil is taken out and cut into a small round electrode plate through a cutting machine.
And assembling the prepared electrode slice into a button cell in a glove box which is filled with high-purity argon and has the water oxygen value of less than or equal to 0.01 ppm. The electrolyte is a solution with Ethylene Carbonate (EC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and 1M LiPF6 as solvents and solutes in a volume ratio of 1:1: 1. The specific method for assembling the battery comprises the following steps: dropping a drop of electrolyte on an electrode shell, placing an electrode plate, then dropping 1 drop of electrolyte, placing a diaphragm, dropping a drop of electrolyte on the diaphragm, placing a lithium sheet as a counter electrode, then respectively placing a gasket and an elastic sheet, pressing and sealing the battery by a hydraulic press, and placing for 8 hours.
Then at 0.5A g-1The results of the cycle performance and charge/discharge performance tests of the button cell are shown in fig. 11, and it can be seen from fig. 11 that the capacity of the cell can still be maintained at about 680mAh/g after 100 cycles.
FIG. 12 shows the binary Co-Ni metal oxide Co prepared in step 2) of example 13O4The NiO and the circulation performance curve of the polyaniline composite material wrapped by the multilayer core-shell structure binary cobalt-nickel metal oxide microspheres prepared in the step 3) show that the composite material wrapped by the polyaniline has good circulation stability. The specific capacity of the binary cobalt-nickel metal oxide of the core-shell structure without being coated with polyaniline is seriously attenuated along with the increase of cycle times, and the performance is optimized and more stable after the polyaniline is coated.
The above detailed description of the binary cobalt-nickel metal oxide-coated polyaniline nanocomposite material with a multi-layer core-shell structure, the preparation method thereof, the negative electrode of the lithium battery and the battery, which have been described above with reference to the embodiments, is illustrative and not restrictive, and several embodiments can be enumerated according to the limited scope, so that changes and modifications without departing from the general concept of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of a multilayer core-shell structure binary cobalt nickel metal oxide coated polyaniline nanocomposite is characterized by comprising the following steps:
1) dissolving a self-template, cobalt salt and nickel salt in water, and carrying out hydrothermal reaction to obtain a binary cobalt-nickel metal oxide carbon microsphere precursor;
2) calcining the binary cobalt nickel metal oxide carbon microsphere precursor obtained in the step 1) at a high temperature in air, and cooling to room temperature to obtain a multilayer core-shell structure binary cobalt nickel oxide microsphere;
3) and (3) coating polyaniline on the multilayer core-shell structure binary cobalt nickel oxide microspheres obtained in the step 2) in an ice bath to obtain the multilayer core-shell structure binary cobalt nickel metal oxide coated polyaniline nanocomposite.
2. The method according to claim 1, wherein in step 1), the ratio of the amounts of glucose, cobalt salt and nickel salt is 14: 10: 5.
3. the method as claimed in claim 1 or 2, wherein the hydrothermal reaction is carried out at 150 ℃ and 180 ℃ for 0.5-8 hours in step 1).
4. The method as claimed in claim 1 or 2, wherein the calcination in step 2) is carried out at 600 ℃ for 1-3 hours.
5. The preparation method according to claim 1 or 2, wherein step 3) is specifically:
3-1) ultrasonically dispersing the binary cobalt nickel metal oxide microspheres with the multilayer core-shell structure obtained in the step 2) in a dilute acid solution, and adding aniline into the dilute acid solution to obtain a solution a;
3-2) dissolving an initiator in a dilute acid solution to obtain a solution b; and (4) dropwise adding the solution b into the solution a, and stirring in an ice bath for reaction.
6. The method according to claim 5, wherein in step 3), the ratio of the amounts of aniline and ammonium persulfate is 2: 1.
7. the preparation method according to claim 5, wherein in step 3-1), the ratio of the amount of binary cobalt-nickel metal oxide microspheres with a multilayer core-shell structure to the amount of aniline is 0.1-0.3: 110-: 50-70 g/mL.
8. The method of claim 1, wherein the ice bath is stirred for 2-12 hours.
9. The multilayer core-shell structure binary cobalt nickel metal oxide-coated polyaniline nanocomposite material prepared by the preparation method of any one of claims 1 to 8, wherein the size of the multilayer core-shell structure binary cobalt nickel metal oxide-coated polyaniline nanocomposite material is 2 to 5 μm.
10. The application of the binary cobalt nickel metal oxide-coated polyaniline nanocomposite material with the multilayer core-shell structure, which is prepared by the preparation method of any one of claims 1 to 8, is characterized by being used for lithium ion batteries.
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Cited By (2)
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| CN115678008A (en) * | 2021-07-28 | 2023-02-03 | 中国科学院大连化学物理研究所 | Nickel oxide-polyaniline composite material and preparation method and application thereof |
| CN113735177A (en) * | 2021-09-06 | 2021-12-03 | 派尔森环保科技有限公司 | Shell-shaped LaFeO with high rate performance of hollow nanospheres3Preparation method of lithium ion battery cathode material |
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