CN110600712A - Carbon and nitrogen Co-doped Co3O4Composite material, preparation method and application thereof - Google Patents
Carbon and nitrogen Co-doped Co3O4Composite material, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses carbon-nitrogen Co-doped Co3O4The composite material is carbon and nitrogen Co-doped Co3O4The particle of the hollow sphere is of a spherical hollow structure, and in an XRD pattern, the 2 theta of the hollow sphere is 19 degrees, 31.3 degrees, 36.9 degrees, 44.8 degrees, 55.7 degrees, 59.4 degrees and 65 degrees.It has a characteristic peak at 2 deg., a C1s XPS spectrum with one peak at 285.1eV of binding energy, and an N1s XPS spectrum with two peaks at 400.2eV and 402.6 eV. The composite material disclosed by the invention can greatly improve the conductivity, specific capacity value and capacity retention rate of the material through a carbon-nitrogen co-doping process, and has good circulation stability.
Description
Technical Field
The invention relates to a composite material, in particular to carbon-nitrogen Co-doped Co3O4Composite material and its preparation method and application.
Background
With the increasing demand of electric automobiles for high-energy density lithium ion batteries, development of lithium ion battery cathode materials with excellent performance is urgently needed. The positive electrode material in the lithium ion battery plays a key role in the specific capacity and energy density of the battery. Over the past decades, various positive electrode materials have been investigated, such as graphite, titanium dioxide, Li4Ti5O12And other metal oxides. Among many positive electrode materials, metal oxides are attracting attention because of their large specific capacity and high energy density.
Using Co3O4Lithium ion batteries as positive electrode materials release higher energy densities than other positive electrode materials. Therefore, researchers are based on Co for development3O4A great deal of effort has been made on the positive electrode material of (1). However, the abnormal capacity fade during electrochemical cycling limits the Co-based3O4The application of the lithium ion battery anode material in the method hinders the commercialization process of the lithium ion battery and the super capacitor. The reasons for poor cycle performance are mainly poor electronic conductivity, low cycle stability and low specific capacity. To improve the cycling stability of lithium ion batteries, various strategies have been used to improve Co3O4The electron conductivity of the base cathode material is not ideal.
Disclosure of Invention
The invention aims to provide carbon-nitrogen Co-doped Co3O4The composite material solves the problem of the existing Co, and the preparation method and the application thereof3O4The material has poor cycle stability, can greatly improve the conductivity, specific capacity value and capacity retention rate of the material through a carbon-nitrogen co-doping process, and has good cycle stability.
In order to achieve the above object, the present invention providesCarbon and nitrogen Co-doped Co3O4The composite material is carbon-nitrogen Co-doped Co3O4A hollow sphere, the particles of which have a spherical hollow structure and have XRD patterns with characteristic peaks at 19 degrees, 31.3 degrees, 36.9 degrees, 44.8 degrees, 55.7 degrees, 59.4 degrees and 65.2 degrees 2 theta, a C1s XPS pattern with one peak at binding energy 285.1eV, and an N1s XPS pattern with two peaks at 400.2eV and 402.6 eV.
Preferably, the composite is made by coating polydopamine in Co3O4And (3) coating the hollow spheres on the hollow spheres, and then keeping the temperature at 750-850 ℃ in an ammonia atmosphere to obtain the hollow spheres.
Preferably, the polydopamine is coated in Co3O4On the hollow ball, the mass ratio of 1: 1.5 to 2.5 of Co3O4The hollow sphere and dopamine hydrochloride are obtained by standing in concentrated hydrochloric acid.
Preferably, the Co3O4The hollow sphere is obtained by carrying out hydrothermal reaction on glucose and cobalt sulfate at 160-190 ℃ to obtain a product, and carrying out heat preservation at 500-580 ℃.
The invention also provides the carbon-nitrogen Co-doped Co3O4A method of preparing a composite material, the method comprising: mixing Co3O4The hollow sphere and dopamine hydrochloride are placed in concentrated hydrochloric acid for standing to obtain polydopamine-coated Co3O4Hollow spheres; co coating the polydopamine3O4The hollow sphere is subjected to heat preservation at 750-850 ℃ in an ammonia atmosphere to obtain carbon-nitrogen Co-doped Co3O4A composite material.
Preferably, the Co3O4The mass ratio of the hollow spheres to the dopamine hydrochloride is 1: 1.5 to 2.5.
Preferably, the concentration of the concentrated hydrochloric acid is 9-11 mol/L; the concentration of the dopamine hydrochloride is 0.5-5 mg/mL.
Preferably, said polydopamine coated Co3O4And (3) insulating the hollow spheres for 1-3 h at 750-850 ℃ in an ammonia atmosphere.
Preferably, the Co3O4Preparation of hollow spheresComprises the following steps: preserving the temperature of the glucose solution at 160-190 ℃, and then adding a mixture of glucose and glucose in a mass ratio of 2-4: 2 glucose and CoSO4·7H2O, performing heat preservation at 160-190 ℃ by adopting a hydrothermal method, heating the obtained product to 500-580 ℃ in an air atmosphere, and performing heat preservation to obtain Co with the particle size of 85-115 nm3O4The hollow ball.
Preferably, the concentration of the glucose solution is 0.3-0.8 mol/L.
Preferably, the glucose solution is kept at 160-190 ℃ for 15-18 h.
Preferably, the hydrothermal method is carried out at 160-190 ℃ for 20-26 h.
Preferably, the temperature rise speed is 1-3 ℃/min.
Preferably, the product is heated to 500-580 ℃ in the air atmosphere and is kept warm for 2-5 h.
The invention also provides the carbon-nitrogen Co-doped Co3O4Use of a composite material for use as a positive electrode active material for a lithium ion battery.
Carbon and nitrogen Co-doped Co of the invention3O4The composite material, the preparation method and the application thereof solve the problem of the prior Co3O4The problem of poor cycle stability has the following advantages:
carbon and nitrogen Co-doped Co of the invention3O4The composite material has a hollow sphere structure, can ensure the stability of the structure in the electrochemical charge and discharge process, greatly improves the conductivity of the material through a carbon-nitrogen co-doping process, and has better specific capacity value and capacity retention rate.
Drawings
FIG. 1 shows carbon-nitrogen Co-doped Co prepared in example 4 of the present invention3O4SEM topography of hollow spheres.
FIG. 2 shows carbon-nitrogen Co-doped Co prepared in example 4 of the present invention3O4TEM topography of hollow spheres.
FIG. 3 shows carbon-nitrogen Co-doped Co prepared in example 4 of the present invention3O4XRD pattern of the hollow sphere.
FIG. 4 shows carbon and nitrogen Co-doped Co prepared in examples 3 and 4 of the present invention3O4Co2p XPS spectra of hollow spheres.
FIG. 5 shows carbon and nitrogen Co-doped Co prepared in examples 3 and 4 of the present invention3O4C1s XPS spectra of hollow spheres.
FIG. 6 shows carbon-nitrogen Co-doped Co prepared in examples 3 and 4 of the present invention3O4N1s XPS spectra of hollow spheres.
FIG. 7 shows carbon-nitrogen Co-doped Co prepared in example 4 of the present invention3O4Hollow spheres and undoped Co3O4CV curve of the hollow sphere.
FIG. 8 shows carbon-nitrogen Co-doped Co prepared in example 4 of the present invention3O4Hollow spheres and undoped Co3O4The curve chart of the charge-discharge cycle performance of the hollow sphere.
FIG. 9 shows carbon-nitrogen Co-doped Co prepared in example 4 of the present invention3O4Hollow spheres and undoped Co3O4The multiplying power performance curve chart of the hollow sphere.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and 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.
Example 1
Carbon and nitrogen Co-doped Co3O4A method of making a composite material comprising:
(1) pouring 0.3mol/L glucose solution into a stainless steel autoclave with a polytetrafluoroethylene lining, preserving the temperature for 15h at 190 ℃, and then adding a mixture of glucose and water in a mass ratio of 4: 2 glucose and CoSO4·7H2O, performing heat preservation for 26 hours at 160 ℃ by adopting a hydrothermal method;
(2) performing centrifugal separation on the product obtained in the step (1), cleaning the product by using water and ethanol in sequence, and drying the product at 70 ℃ for 7 hours;
(3) putting the product obtained in the step (2) in an air atmosphere, heating the product by using a tube furnace at the heating rate of 1 ℃/min to 580 ℃ and preserving the heat for 2h to obtain Co with the average particle size of 100 (+/-15) nm3O4Hollow spheres;
(4) mixing the components in a mass ratio of 1: 1.5 Co prepared in step (3)3O4And 5mg/mL dopamine hydrochloride (Shenzhen proekang biotechnology Limited) is dissolved in concentrated hydrochloric acid with the concentration of 9mol/L, and after standing for 5 hours, the Polydopamine (PDA) -coated Co is successfully prepared3O4A composite material;
(5) co coated with Polydopamine (PDA) prepared in step (4)3O4Placing the composite material in NH3Heating to 750 ℃ in the atmosphere, preserving heat for 3h, naturally cooling to room temperature, washing with absolute ethyl alcohol until the pH value is 7, and drying at 50 ℃ to obtain carbon-nitrogen Co-doped Co3O4A composite material.
Example 2
Carbon and nitrogen Co-doped Co3O4The preparation method of the composite material is basically the same as that of the embodiment, and the difference is that:
in the step (1), the concentration of the glucose solution is 0.8mol/L, and the temperature is kept for 18h at 160 ℃ in a stainless steel autoclave; glucose and CoSO4·7H2The mass ratio of O is 2: 2, carrying out heat preservation for 20 hours at 190 ℃ by a hydrothermal method;
in the step (2), the drying temperature is 90 ℃, and the drying time is 4 hours;
in the step (3), the heating rate is 3 ℃/min, the heating is carried out to 500 ℃, and the heat preservation time is 5 h;
in the step (4), the concentration of the dopamine hydrochloride is 0.5mg/mL, and the Co content is3O4The mass ratio of the hollow spheres to the dopamine hydrochloride is 1: 2.5, keeping the concentration of concentrated hydrochloric acid at 11mol/L, and standing for 3 hours;
in step (5), in NH3Heating to 850 ℃ under the atmosphere, keeping the temperature for 1h, and drying at 70 ℃.
Example 3
Carbon and nitrogen Co-doped Co3O4The preparation method of the composite material is basically the same as that of the embodiment, and the difference is that:
in the step (1), the concentration of the glucose solution is 0.5mol/L, and the temperature is kept for 16h at 180 ℃ in a stainless steel autoclave; glucose and CoSO4·7H2The mass ratio of O is 3: 2, carrying out heat preservation for 23 hours at 170 ℃ by a hydrothermal method;
in the step (2), the drying temperature is 80 ℃, and the drying time is 5 hours;
in the step (3), the heating rate is 2 ℃/min, the temperature is heated to 540 ℃, and the heat preservation time is 4 h;
in the step (4), the concentration of the dopamine hydrochloride is 3mg/mL, and the Co content is3O4The mass ratio of the hollow spheres to the dopamine hydrochloride is 1: 2, standing for 4 hours with the concentration of concentrated hydrochloric acid of 10 mol/L;
in step (5), in NH3Heating to 800 ℃ under the atmosphere, keeping the temperature for 2h, and drying at 60 ℃.
Example 4
Carbon and nitrogen Co-doped Co3O4The preparation method of the composite material is basically the same as that of the embodiment, and the difference is that:
in the step (1), the concentration of the glucose solution is 0.5mol/L, and the temperature is kept for 16h at 180 ℃ in a stainless steel autoclave; glucose and CoSO4·7H2The mass ratio of O is 3: 2, carrying out heat preservation for 24 hours at 180 ℃ by a hydrothermal method;
in the step (2), the drying temperature is 80 ℃, and the drying time is 5 hours;
in the step (3), the heating rate is 2 ℃/min, the heating is carried out to 550 ℃, and the heat preservation time is 3 h;
in the step (4), the concentration of the dopamine hydrochloride is 4mg/mL, and the Co content is3O4The mass ratio of the hollow spheres to the dopamine hydrochloride is 1: 2, standing for 3 hours with the concentration of concentrated hydrochloric acid of 10 mol/L;
in step (5), in NH3Heating to 800 ℃ under the atmosphere, keeping the temperature for 1h, and drying at 60 ℃.
As shown in FIG. 1, it is carbon-nitrogen Co-doped Co prepared in example 4 of the present invention3O4The SEM topography of the hollow sphere shows that the particles are spherical, uniform in size and smooth in surface. As shown in FIG. 2, it is carbon-nitrogen Co-doped Co prepared in example 4 of the present invention3O4The TEM morphology of the hollow sphere shows that the particles are in a spherical stable hollow structure.
As shown in FIG. 3, the carbon-nitrogen Co-doped Co prepared in example 4 of the present invention3O4The XRD pattern of the hollow sphere can be seen from the figure, the hollow sphere has characteristic peaks at the 2 theta of 19 degrees, 31.3 degrees, 36.9 degrees, 44.8 degrees, 55.7 degrees, 59.4 degrees and 65.2 degrees, and compared with a JCPDS42-1467 standard card, the prepared carbon-nitrogen Co-doped Co-based material has the advantages of high carbon-nitrogen Co-doped Co-based material and low carbon-nitrogen Co-doped Co-based material3O4The composite material shows typical Co3O4Diffraction peaks, which indicate that C and N elements have been successfully incorporated into Co3O4In (1).
As shown in FIG. 4, carbon and nitrogen Co-doped Co prepared for examples 3 and 4 of the present invention3O4Co2p XPS spectra of hollow spheres, from which it can be seen that carbon and nitrogen Co-doped Co prepared in examples 3 and 43O4The hollow sphere has two main peaks at 781.2ev and 796.8ev, and the two peaks respectively correspond to Co2p3/2And Co2p1/2。
As shown in FIG. 5, carbon and nitrogen Co-doped Co prepared in examples 3 and 4 of the present invention3O4The C1s XPS spectrum of the hollow sphere shows that a peak exists at 285.1eV binding energy, which represents C and N codoped Co3O4C-C bond in spherical complexes.
As shown in FIG. 6, carbon and nitrogen Co-doped Co prepared for examples 3 and 4 of the present invention3O4N1s XPS spectra of hollow spheres, from which it can be seen that carbon and nitrogen Co-doped Co prepared in examples 3 and 43O4The hollow sphere had two peaks at 400.2eV and 402.6eV, which correspond to the Co-N bond and N1s, respectively, indicating that C and N have been doped into Co3O4The hollow ball.
For the carbon and nitrogen Co-doped Co prepared in the embodiment 4 of the invention3O4The hollow sphere is subjected to electrochemical performance test, which specifically comprises the following steps:
assembling the Coin 2032 half-cell, lithium film andcarbon and nitrogen Co-doped Co prepared in example 43O4The hollow spheres are respectively used as a negative electrode and a positive electrode, the diaphragm is Celgard 2300, and the electrolyte is 1.0mol/L LiPF6And EC/DEC (ethylene carbonate/diethyl carbonate), and a constant current discharge and constant current charge curve test of 0 to 3V was performed on a battery tester (LAND CT2001A), and a CV curve test was performed on an electrochemical station (CHI 660E).
As shown in FIG. 7, the carbon-nitrogen Co-doped Co prepared in example 4 of the present invention3O4Hollow spheres and undoped Co3O4CV plot of the hollow spheres, it can be seen that undoped Co3O4Two characteristic peaks of the hollow sphere are obviously smaller than those of carbon and nitrogen Co-doped Co3O4Hollow sphere, carbon and nitrogen Co-doped Co3O4The material has excellent charge and discharge performance.
As shown in FIG. 8, it is carbon-nitrogen Co-doped Co prepared in example 4 of the present invention3O4Hollow spheres and undoped Co3O4The charge-discharge cycle performance curve chart of the hollow sphere shows that when the current density is 0.1c, carbon and nitrogen are codoped with Co3O4The specific capacity value and the capacity retention rate are higher, which shows that the catalyst has good cycle stability.
As shown in FIG. 9, which is the carbon-nitrogen Co-doped Co prepared in example 4 of the present invention3O4Hollow spheres and undoped Co3O4The multiplying power performance curve chart of the hollow sphere shows that carbon and nitrogen Co-doped Co3O4The positive electrode material shows excellent performance under different current densities.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (10)
1. Carbon and nitrogen Co-doped Co3O4The composite material is characterized by being carbon-nitrogen Co-doped Co3O4A hollow sphere, the particles of which have a spherical hollow structure and have XRD patterns with characteristic peaks at 19 degrees, 31.3 degrees, 36.9 degrees, 44.8 degrees, 55.7 degrees, 59.4 degrees and 65.2 degrees 2 theta, a C1s XPS pattern with one peak at binding energy 285.1eV, and an N1s XPS pattern with two peaks at 400.2eV and 402.6 eV.
2. Carbon and nitrogen Co-doped Co according to claim 13O4A composite material, characterized in that the composite material is obtained by coating polydopamine on Co3O4And (3) coating the hollow spheres on the hollow spheres, and then keeping the temperature at 750-850 ℃ in an ammonia atmosphere to obtain the hollow spheres.
3. Carbon and nitrogen Co-doped Co according to claim 23O4Composite material, characterized in that said polydopamine is coated in Co3O4On the hollow ball, the mass ratio of 1: 1.5 to 2.5 of Co3O4The hollow sphere and dopamine hydrochloride are obtained by standing in concentrated hydrochloric acid.
4. Carbon and nitrogen Co-doped Co according to claim 23O4Composite material, characterized in that said Co3O4The hollow sphere is obtained by carrying out hydrothermal reaction on glucose and cobalt sulfate at 160-190 ℃ to obtain a product, and carrying out heat preservation at 500-580 ℃.
5. Carbon and nitrogen Co-doped Co as claimed in any one of claims 1 to 43O4A method of making a composite material, the method comprising:
mixing Co3O4The hollow sphere and dopamine hydrochloride are placed in concentrated hydrochloric acid for standing to obtain polydopamine-coated Co3O4Hollow spheres;
co coating the polydopamine3O4The hollow sphere is subjected to heat preservation at 750-850 ℃ in an ammonia atmosphere to obtain carbon-nitrogen Co-doped Co3O4A composite material.
6. Carbon nitrogen Co-doped Co according to claim 53O4The preparation method of the composite material is characterized in that the Co3O4The mass ratio of the hollow spheres to the dopamine hydrochloride is 1: 1.5 to 2.5.
7. Carbon nitrogen Co-doped Co according to claim 53O4The preparation method of the composite material is characterized in that the concentration of the concentrated hydrochloric acid is 9-11 mol/L; the concentration of the dopamine hydrochloride is 0.5-5 mg/mL.
8. Carbon nitrogen Co-doped Co according to claim 53O4A method for preparing a composite material, characterized in that said polydopamine coated Co3O4And (3) insulating the hollow spheres for 1-3 h at 750-850 ℃ in an ammonia atmosphere.
9. Carbon nitrogen Co-doped Co according to any one of claims 5 to 83O4The preparation method of the composite material is characterized in that the Co3O4The preparation of the hollow sphere comprises the following steps: preserving the temperature of the glucose solution at 160-190 ℃, and then adding a mixture of glucose and glucose in a mass ratio of 2-4: 2 glucose and CoSO4·7H2O, performing heat preservation at 160-190 ℃ by adopting a hydrothermal method, heating the obtained product to 500-580 ℃ in an air atmosphere, and performing heat preservation to obtain Co with the particle size of 85-115 nm3O4The hollow ball.
10. Carbon and nitrogen Co-doped Co as claimed in any one of claims 1 to 43O4Use of a composite material, characterized in that the composite material is used as a positive electrode active material for a lithium ion battery.
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| CN111834636A (en) * | 2020-07-21 | 2020-10-27 | 陕西师范大学 | Preparation method of nitrogen-doped TiO lithium-sulfur battery positive electrode carrier with large specific surface area |
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| CN111834636B (en) * | 2020-07-21 | 2021-11-02 | 陕西师范大学 | Preparation method of nitrogen-doped TiO lithium-sulfur battery positive electrode carrier with large specific surface area |
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