CN114899382A - N-doped porous carbon double-shell microsphere structure coated Co 3 O 4 Material, preparation method and application thereof - Google Patents
N-doped porous carbon double-shell microsphere structure coated Co 3 O 4 Material, 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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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention relates to the technical field of lithium ion battery cathode materials, and discloses an N-doped porous carbon double-shell microsphere structure coated Co 3 O 4 A material and a preparation method and application thereof. The method comprises the following steps: (1) adding cobalt salt and a surfactant into a first solvent for dissolving; (2) atomizing the mixed solution, and then introducing the atomized mixed solution into a high-temperature furnace for pyrolysis to obtain precursor powder; (3) ultrasonically dispersing the precursor powder into a second solvent, mixing, adding dimethyl imidazole for ultrasonic treatment, and stirring for reaction; after the reaction is finished, respectively washing the sample by using water and ethanol in a centrifugal way, and drying the obtained sample in a vacuum drying oven; (4) calcining the product under protective gas to obtain the N-doped porous carbon double-shell microsphere structure coated Co 3 O 4 A material. The reserved space synchronously formed between the double shells of the material provides more lithium storage sites; multiple continuous active channels are constructed between the double shells, so that the conductivity and stability of the electrode are improved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a Co-coated N-doped porous carbon double-shell microsphere structure 3 O 4 A material, a preparation method and application thereof.
Background
The lithium ion battery can provide higher performanceMass and volumetric energy density have been widely used in the fields of portable electronic products, electric vehicles, etc., as one of the most widely utilized electrochemical energy storage devices. However, due to the relatively low theoretical capacity of conventional graphite anodes, the performance limits of commercial lithium ion batteries have been reached. Thus transition metal oxides (e.g. MnO, MnO) 2 、Fe 2 O 3 、Fe 3 O 4 、 CoO、Co 3 O 4 NiO, CuO, etc.) all provide better options for developing anode materials that can provide higher energy densities and longer cycle lives due to higher theoretical capacities. In particular Co 3 O 4 Due to excellent physical and electrochemical properties, the lithium ion battery can meet the requirements of high-performance lithium ion batteries, and therefore scientific researchers are welcomed. Unfortunately, intrinsic conductivity defects, as well as volume collapse induced during lithium ion intercalation/deintercalation, lead to rapid degradation of cycling capacity caused by electrode dusting and agglomeration. In order to solve this problem, various methods have been adopted, mainly divided into two basic strategies, i.e., structural regulation, and the preparation of a multi-level layered structure by various means, thereby improving the lithium storage capacity. The construction of the special structures not only increases additional lithium storage sites and promotes the occurrence of new lithium storage mechanism reactions, but also accelerates the diffusion rate of lithium ions and relieves volume expansion, thereby showing unique performance as an anode material. However, the regulation and control of the structure has a very limited effect on improving the electronic conductivity, so that the optimization of the components also plays an important role. By using highly conductive materials (carbon nanotubes, nanofibers, graphene, etc.) with Co 3 O 4 Preparation of composite materials to shorten Li + The diffusion path accelerates the reaction kinetics rate and improves the electronic conductivity of the overall composite material. It is inevitable, however, that the specific capacity of a high content of conductive material is always lower compared to pure Transition Metal Oxides (TMOs). Therefore, work was undertaken with a view to combining structural regulation with component optimization to achieve unexpected results.
Based on the structure, the invention provides the N-doped porous carbon double-shell microsphere structure coated Co with the additional space and multiple continuous active channels 3 O 4 Electrode materials, which have not been reported.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a Co-coated N-doped porous carbon double-shell microsphere structure 3 O 4 The material, the preparation method and the application thereof expand the strategy of the composite transition metal oxide material in constructing the continuous Li + channel between the effective reserved space and the interface, and meanwhile, the design deeply grasps the size effect of the composite material and the dynamic balance of the effective channel site. The method has the advantages of novel design idea, high prospect, simple operation, high yield and low cost, and can greatly improve the application performance of the lithium ion battery.
In order to achieve the purpose, the invention provides a Co-coated N-doped porous carbon double-shell microsphere structure 3 O 4 A method of preparing a material, the method comprising the steps of:
(1) adding a cobalt salt and a surfactant into a first solvent for dissolving to obtain a mixed solution;
(2) atomizing the mixed solution, and then introducing the atomized mixed solution into a high-temperature furnace for pyrolysis to obtain precursor powder;
(3) ultrasonically dispersing the precursor powder into a second solvent, mixing, adding dimethyl imidazole for ultrasonic treatment, and stirring for reaction; after the reaction is finished, respectively washing the sample by using water and ethanol in a centrifugal way, and drying the obtained sample in a vacuum drying oven;
(4) calcining the product obtained in the step (3) under protective gas to obtain the Co coated with the N-doped porous carbon double-shell microsphere structure 3 O 4 A material.
Preferably, in the step (1), the cobalt salt is at least one of cobalt nitrate, cobalt chloride and cobalt acetate.
Preferably, the surfactant is at least one of PVP, SDBS and F127.
Preferably, the first solvent is water.
Preferably, in step (1), the molar ratio of the cobalt salt to the surfactant is 8:0.1 to 8, more preferably 8:1 to 3.
Preferably, the concentration of the cobalt ions in the mixed solution is 0.01-0.5 mol/L.
Preferably, in the step (2), the pyrolysis temperature is 350-650 ℃.
Preferably, in step (3), the second solvent is deionized water and/or absolute ethanol.
Preferably, in the step (3), the mass ratio of the precursor powder to the dimethyl imidazole is 1: 1-20.
Preferably, in the step (3), the stirring time is 1 to 6 hours.
Preferably, in step (4), the calcination conditions are: the temperature is 400-700 ℃, and the heating rate is 1.5-2.5 ℃/min.
The invention provides a second aspect of the invention, which provides a Co-coated N-doped porous carbon double-shell microsphere structure 3 O 4 The material is characterized in that the N-doped porous carbon double-shell microsphere structure is coated with Co 3 O 4 The material was prepared by the method described previously.
In a third aspect of the invention, the N-doped porous carbon double-shell microsphere structure coated with Co is provided 3 O 4 The material is applied to the negative electrode material of the lithium ion battery.
Compared with the prior art, the invention has at least the following advantages:
1) the method has the advantages of novel design thought, simple equipment, low cost, high yield and suitability for industrial production; moreover, the method can be completed only by using a high-temperature furnace and some conventional instruments.
2) The method expands the strategy of the composite transition metal oxide material in constructing the effective reserved space and the continuous Li + channel between the interfaces, is easy to operate, and can be completed by only adopting two steps of a spray pyrolysis method and an in-situ grown additional carbon layer.
3) The material has a special nitrogen-carbon double-shell microsphere structure, provides a better constraint effect, and greatly relieves the volume expansion effect; the reserved space synchronously formed between the double shells provides more lithium storage sites; multiple continuous active channels are constructed between the double shells, so that the conductivity and stability of the electrode are improved.
4) The material has high initial discharge capacity, large specific capacity and good cycling stability. The material is 0.2Ag -1 2183.1mAhg was obtained -1 The capacity after 250 cycles is 1121.36mAhg -1 At 1Ag -1 The long-term capacity retention rate after 700 times of lower circulation is approximately equal to 92.4 percent.
5) The nitrogen doping belongs to one of the hetero atoms, and the main purpose of the N doping is to improve the conductivity of the material, because the nitrogen doping can provide an ion channel to be enlarged and enhance the conductivity. The nitrogen-doped porous carbon is synchronously generated and is derived from a reagent dimethyl imidazole, no additional experimental conditions are required to be added, and the operation is simple; other elements are doped, but additional experimental conditions are needed, so that the method is complicated and cannot be realized by adopting the method provided by the invention.
Drawings
FIG. 1 shows that the N-doped porous carbon double-shell microsphere structure obtained in example 1 is coated with Co 3 O 4 Scanning Electron Microscope (SEM) pictures of the material.
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of the Co3O4 double-shell microsphere material obtained in example 1.
FIG. 3 shows that the N-doped porous carbon double-shell microsphere structure obtained in example 1 is coated with Co 3 O 4 X-ray diffraction analysis (XRD) pattern of the material.
FIG. 4 shows that the N-doped porous carbon double-shell microsphere structure obtained in example 1 is coated with Co 3 O 4 Cyclic voltammogram (0.2m Vs) for material-assembled 2032-type button cells -1 )。
FIG. 5 shows that the N-doped porous carbon double-shell microsphere structure obtained in example 1 is coated with Co 3 O 4 Charge and discharge curves (0.2A) for a 2032 type button cell assembled of materials.
FIG. 6 shows that the N-doped porous carbon double-shell microsphere structure obtained in example 1 is coated with Co 3 O 4 Cycling curve (0.2A) for material assembled type 2032 button cell.
FIG. 7 shows that the N-doped porous carbon double-shell microsphere structure obtained in example 1 is coated with Co 3 O 4 2032 type material assembledCycling curve of button cell (1A).
Fig. 8 is a Scanning Electron Microscope (SEM) photograph of the resulting material using glucose as a carbon source.
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
On the one hand, the invention provides a Co-coated N-doped porous carbon double-shell microsphere structure 3 O 4 A method of preparing a material, the method comprising the steps of:
(1) adding a cobalt salt and a surfactant into a first solvent for dissolving to obtain a mixed solution;
(2) atomizing the mixed solution, and then introducing the atomized mixed solution into a high-temperature furnace for pyrolysis to obtain precursor powder;
(3) ultrasonically dispersing the precursor powder into a second solvent, mixing, adding dimethyl imidazole for ultrasonic treatment, and stirring for reaction; after the reaction is finished, respectively washing the sample by using water and ethanol in a centrifugal way, and drying the obtained sample in a vacuum drying oven;
(4) calcining the product obtained in the step (3) under protective gas to obtain the Co coated with the N-doped porous carbon double-shell microsphere structure 3 O 4 A material.
In the method, aerosol formed by atomizing a mixed solution of cobalt salt and a surfactant is pyrolyzed in a high-temperature furnace, the cobalt salt is heated and decomposed into metal oxide, and the surfactant is heated and decomposed into amorphous carbon to obtain precursor powder; then adding dimethyl to the precursor powder solutionUltrasonically mixing imidazole, stirring for reaction, centrifugally washing a sample, and drying; calcining the dried product to obtain the N-doped porous carbon double-shell microsphere structure coated Co 3 O 4 A material.
The method firstly adopts a spray pyrolysis method to synthesize Co 3 O 4 Hollow spheres compounded with carbon, then dimethylimidazole can pass through the pores, with the inner shell Co 3 O 4 React with and deprotonate the generated H + to thereby yield a small amount of Co 3 O 4 Dissolving to produce Co 2+ . On the outer surface of ZIF-67 layer, Co 2+ Ions diffuse outwards to react with a large amount of ligand dimethyl imidazole, so that continuous growth is realized, and a nitrogen-carbon double-shell structure with certain pores is obtained through high-temperature calcination. The stirring function is as follows: dissolving Co of the inner shell part 3 O 4 Thereby forming Co 2+ And further generation of the shell is realized.
In a specific embodiment, in step (1), the cobalt salt is at least one of cobalt nitrate, cobalt chloride and cobalt acetate. In a preferred embodiment, the cobalt salt is cobalt nitrate.
In the method, in order to effectively control the tension of the precursor solution and promote the dispersion of metal ions, thereby controlling the uniformity of the morphology, element components and size of the material, a surfactant is used as a source of the amorphous carbon. In particular embodiments, the surfactant may be at least one of PVP, SDBS, and F127. In a preferred embodiment, the surfactant is PVP. In the present invention, PVP having a molecular weight of 8000, 58000 or 1300000, preferably PVP having a molecular weight of 58000, may be employed.
In the present invention, other carbon sources, such as glucose, are used, and the obtained material has too large size difference and non-uniform morphology (as shown in fig. 8, the diameter of each sphere in the electron micrograph is very different), which further affects the cycle performance of the material.
In a specific embodiment, the first solvent is water.
In the process according to the invention, the properties of the material are seriously affected by the ratio between the carbon content and the metal, for example: the charge/discharge capacity of the material is decreased by a large carbon content. Therefore, the proportional relationship between carbon and metal ions needs to be reasonably understood, and the proportional relationship between the cobalt salt and the surfactant needs to be controlled within an appropriate range.
In a specific embodiment, in step (1), the molar ratio of the cobalt salt to the surfactant may be 8:0.1 to 8, for example 8:0.1, 8:1, 8:2, 8:3, 8:4, 8:5, 8:6, 8:7 or 8:8, preferably 8:1 to 3. In a specific embodiment, the concentration of cobalt ions in the mixed solution may be 0.01 to 0.5mol/L, for example, 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, or 0.5 mol/L.
In a more preferred embodiment, in the step (1), the molar ratio of the cobalt salt to the surfactant is 8:2, and the concentration of cobalt ions in the mixed solution is 0.5 mol/L.
In the process according to the invention, the cobaltosic oxide obtained after calcination has the highest theoretical capacity, but different calcination temperatures lead to cobalt-based oxides of other phases, for example: cobalt oxide, cobaltosic oxide, etc., and thus the pyrolysis temperature needs to be controlled within a suitable range in order to obtain a definite product, cobaltosic oxide. In a specific embodiment, in step (2), the pyrolysis temperature is 350 to 650 ℃, for example 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ or 650 ℃. In a preferred embodiment, the pyrolysis temperature is 500 ℃.
In specific embodiments, in step (3), the second solvent may be deionized water, absolute ethanol, or a mixture of deionized water and absolute ethanol. In a preferred embodiment, the second solvent may be a mixture of deionized water and absolute ethanol in a volume ratio of 1: 1.
In the method of the present invention, the ratio of the precursor powder to the dimethylimidazole needs to be controlled within a suitable range. In a specific embodiment, in the step (3), the mass ratio of the precursor powder to the dimethylimidazole may be 1:1 to 20, for example, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18, or 1: 20. In a preferred embodiment, in step (3), the mass ratio of the precursor powder to dimethylimidazole may be 1: 10.
In a specific embodiment, in the step (3), the stirring time may be 1 to 6 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, or 6 hours. In a preferred embodiment, in step (3), the stirring time is 3 hours.
In the method of the present invention, firstly, in order to confirm that the product is tricobalt tetraoxide; secondly, because carbon can be pyrolyzed at a certain temperature, the content of carbon is not greatly lost due to pyrolysis under the condition that the product is cobaltosic oxide, and the calcining condition needs to be reasonably controlled. In a specific embodiment, in step (4), the calcination conditions may be: the temperature is 400 to 700 ℃, for example 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ or 700 ℃; the temperature rise rate is 1.5-2.5 ℃/min, such as 1.5 ℃/min, 1.6 ℃/min, 1.7 ℃/min, 1.8 ℃/min, 1.9 ℃/min, 2 ℃/min, 2.1 ℃/min, 2.2 ℃/min, 2.3 ℃/min, 2.4 ℃/min or 2.5 ℃/min. In a preferred embodiment, in step (4), the temperature of the calcination is 500 ℃.
The invention provides a second aspect of the invention, which provides a Co-coated N-doped porous carbon double-shell microsphere structure 3 O 4 The material is characterized in that the N-doped porous carbon double-shell microsphere structure is coated with Co 3 O 4 The material was prepared by the method described previously.
In a third aspect of the invention, the N-doped porous carbon double-shell microsphere structure coated with Co is provided 3 O 4 The material is applied to the negative electrode material of the lithium ion battery.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
The electrical property test process of the invention is as follows: the materials obtained in the examples and the comparative examples, the super P-Li conductive carbon black and the PVDF adhesive are fully ground and mixed evenly according to the proportion of 70 percent to 20 percent to 10 percent respectively, and are mixed into uniform slurry to be coated on Cu foil, dried and compacted. Assembling into 2032 type button type in glove box with high purity argon (purity greater than 99.99%) atmosphereBattery (H) 2 O content less than 1ppm, O 2 Content less than 3ppm), wherein the lithium metal sheet is used as a negative electrode, and the electrical properties of the material are tested.
Example 1
(1) Adding cobalt nitrate and PVP into 40mL of deionized water, wherein the molar ratio of the cobalt nitrate to the PVP is 8:2, stirring for 30 minutes to obtain a mixed solution, wherein the concentration of cobalt ions in the mixed solution is 0.5 mol/L;
(2) introducing aerosol formed by atomizing the mixed solution into a high-temperature furnace for pyrolysis at 500 ℃, collecting powder at the other end by using a filtering device under the suction action of a vacuum pump, and drying the obtained sample at 60 ℃ for 12 hours to obtain precursor powder;
(3) ultrasonically dispersing 0.1g of the precursor powder into 10.0mL of deionized water and 10.0mL of ethanol, uniformly stirring, adding 1.0g of dimethyl imidazole, performing ultrasonic treatment for 30min to obtain a uniform mixed solution, and then stirring for 3h at room temperature for reaction; after the reaction is finished, centrifugally washing the sample for 3 times by using water and ethanol respectively, and drying the obtained sample in a vacuum drying oven for 12 hours;
(4) calcining the product obtained in the step (3) at 500 ℃ for 4 hours in an argon atmosphere, wherein the temperature is raised to 500 ℃ at the temperature rise rate of 2 ℃/min to obtain the N-doped porous carbon double-shell microsphere structure coated Co 3 O 4 A material.
0.2Ag in example 1 -1 The initial discharge capacity at this time was 2183.5mAhg -1 ，0.2Ag -1 The capacity after 250 times of lower circulation is 1121.36mAhg -1 ；1Ag -1 The initial discharge capacity at this time was 732.24mAhg -1 ，1Ag -1 The capacity after 700 times of circulation is 667.41mAhg -1 。
As can be seen from fig. 1 and 2, the prepared material forms a double-shell structure.
Example 2
The procedure of example 1 was followed except that the molar ratio of cobalt nitrate to PVP was 8: 4.
Example 2 0.2Ag -1 The initial discharge capacity at this time was 1380.9mAhg -1 ，0.2Ag -1 The capacity after 150 times of lower circulation is 924.86mAhg -1 ；1Ag -1 The initial discharge capacity at this time was 666.89mAhg -1 ，1Ag -1 The capacity after 200 times of circulation is 405.9mAhg -1 。
Example 3
The procedure of example 1 was followed except that the molar ratio of cobalt nitrate to PVP was 8: 8.
Example 3 0.2Ag -1 The initial discharge capacity at this time was 943.2mAhg -1 ，0.2Ag -1 The capacity after the next circulation is 150 times is 841.5mAhg -1 ；1Ag -1 The initial discharge capacity at this time was 545.8787mAhg -1 ，1Ag -1 The capacity after 200 times of circulation is 354.38mAhg -1 。
Comparative example
The procedure of example 1 was followed except that the molar ratio of cobalt nitrate to PVP was 8:0.
0.2Ag in comparative example -1 The initial discharge capacity at this time was 1110.1mAhg -1 ，0.2Ag -1 The capacity after 150 times of lower circulation is 539.2mAhg -1 ；1Ag -1 The initial discharge capacity at this time was 585.68mAhg -1 ，1Ag -1 The capacity after 200 times of circulation is 189.39mAhg -1 . Amorphous carbon was not obtained when the method of comparative example was carried out, indicating that the presence of carbon can improve the cycle stability and conductivity of the material.
It can be seen from the examples and comparative examples that the cycle performance of the materials prepared according to the methods described in the examples is significantly higher than that of the comparative examples.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. N-doped porous carbon double-shell microsphere structure coated Co 3 O 4 A method for preparing a material, characterized in that said methodThe method comprises the following steps:
(1) adding a cobalt salt and a surfactant into a first solvent for dissolving to obtain a mixed solution;
(2) atomizing the mixed solution, and then introducing the atomized mixed solution into a high-temperature furnace for pyrolysis to obtain precursor powder;
(3) ultrasonically dispersing the precursor powder into a second solvent, mixing, adding dimethyl imidazole for ultrasonic treatment, and stirring for reaction; after the reaction is finished, respectively washing the sample by using water and ethanol in a centrifugal way, and drying the obtained sample in a vacuum drying oven;
(4) calcining the product obtained in the step (3) under protective gas to obtain the Co coated with the N-doped porous carbon double-shell microsphere structure 3 O 4 A material.
2. The method according to claim 1, wherein in step (1), the cobalt salt is at least one of cobalt nitrate, cobalt chloride and cobalt acetate;
preferably, the surfactant is at least one of PVP, SDBS and F127;
preferably, the first solvent is water.
3. The process according to claim 1 or 2, characterized in that in step (1), the molar ratio of the cobalt salt to the surfactant is 8: 0.1-8, preferably 8: 1-3;
preferably, the concentration of the cobalt ions in the mixed solution is 0.01-0.5 mol/L.
4. The method according to claim 1, wherein in the step (2), the pyrolysis temperature is 350 to 650 ℃.
5. The method according to claim 1, wherein in step (3), the second solvent is deionized water and/or absolute ethanol.
6. The method according to claim 1, wherein in the step (3), the mass ratio of the precursor powder to the dimethylimidazole is 1: 1-20.
7. The method according to claim 1, wherein in the step (3), the stirring time is 1 to 6 hours.
8. The method according to claim 1, wherein in step (4), the calcination conditions are: the temperature is 400-700 ℃, and the heating rate is 1.5-2.5 ℃/min.
9. N-doped porous carbon double-shell microsphere structure coated Co 3 O 4 The material is characterized in that the N-doped porous carbon double-shell microsphere structure is coated with Co 3 O 4 The material is prepared by the method of any one of claims 1-8.
10. The N-doped porous carbon double-shell microsphere structure coated Co of claim 9 3 O 4 The material is applied to the negative electrode material of the lithium ion battery.
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