CN108682829B - Preparation method of nitrogen-doped carbon-coated silicon composite graphite material - Google Patents
Preparation method of nitrogen-doped carbon-coated silicon composite graphite material Download PDFInfo
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Classifications
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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 belongs to the technical field of lithium ion batteries, and relates to a preparation method of a nitrogen-doped carbon-coated silicon composite graphite material, which comprises the following steps: the preparation method comprises the steps of taking melamine as a nitrogen source, organic acid as a carbon source and modified graphene as a conductive bridge, uniformly mixing the melamine, the organic acid, the modified graphene and a nano-silicon turbid liquid, then adding graphite, uniformly mixing and drying; grinding and sieving the mixed dry material, transferring the material to a rotary furnace, introducing inert atmosphere, heating to 100-500 ℃, and embedding the nano silicon particles into functional structure components generated in situ after the reaction of melamine, organic acid and modified graphene; then the temperature is continuously increased for carbonization. Compared with the prior art, the silicon-carbon composite material is obtained by coating the silicon composite graphite material with the in-situ nitrogen-doped carbon, and the material has the advantages of obviously improved cycle performance and good rate capability. And the method is simple, low in cost and very suitable for large-scale production and application.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a preparation method of a nitrogen-doped carbon-coated silicon composite graphite material.
Background
In recent years, due to the continuous development of the field of electric automobiles, the energy density of a single battery is required to reach 300wh/kg in a planning target in 2020, which is a great challenge for a traditional lithium ion battery adopting graphite (with a theoretical gram capacity of 372mAh/g) as a negative electrode, proposed by the four departments of industry and trust at present in the scheme of promoting the development action of the automobile power battery industry. While silicon has a theoretical capacity of 4200mAh/g and a low de-intercalation plateau (< 0.5V Vs Li/Li)+) Silicon-based materials are expected to be one of the mainstream materials of the next-generation lithium ion negative electrode materials. However, silicon-based materials have a fatal disadvantage: in the process of extracting lithium ions from a silicon material, the volume change is large, which easily causes pulverization of an electrode material and deterioration of electrode performance, thereby making battery cycle performance poor.
In view of the above, the present invention aims to provide a method for preparing a nitrogen-doped carbon-coated silicon composite graphite material, wherein the silicon-carbon composite material is obtained by using an in-situ nitrogen-doped carbon-coated silicon composite graphite material, and the material has the advantages of significantly improved cycle performance and good rate capability. And the method is simple, low in cost and very suitable for large-scale production and application.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the preparation method of the nitrogen-doped carbon-coated silicon composite graphite material is provided, the in-situ nitrogen-doped carbon-coated silicon composite graphite material is adopted, so that the silicon-carbon composite material is obtained, the cycle performance of the material is obviously improved, and the multiplying power performance is good. And the method is simple, low in cost and very suitable for large-scale production and application.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nitrogen-doped carbon-coated silicon composite graphite material at least comprises the following steps:
step one, melamine with high nitrogen content is used as a nitrogen source, organic acid is used as a carbon source, modified graphene is used as a conductive bridge, the melamine, the organic acid, the modified graphene and the nano-silicon turbid liquid are uniformly mixed, then graphite is added, and the mixture is uniformly mixed and dried;
and step two, grinding and sieving the dried material mixed in the step one, then transferring the material to a rotary furnace, introducing inert atmosphere, heating to 100-500 ℃, preserving heat for 0.1-5 h, and reacting amino of melamine with organic acid and carboxyl in modified graphene respectively to generate a functional structure component containing C-N bonds, wherein the carboxyl of the organic acid and hydroxyl in the modified graphene generate esters. The nano silicon particles are embedded into functional structure components generated in situ after reaction of melamine, organic acid and modified graphene; and then continuously heating to 500-1000 ℃, carbonizing the functional structure components for 0.5-24 h, removing oxygen and hydrogen in the functional structure, cooling, scattering and sieving to obtain the compact nitrogen-doped carbon-coated silicon composite graphite material.
As an improvement of the preparation method of the nitrogen-doped carbon-coated silicon composite graphite material, the nitrogen-doped carbon-coated silicon composite graphite material obtained in the step two has a core-shell structure, the shell layer is a nitrogen-doped carbon layer embedded with nano-silicon, the core layer is graphite, and the nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after the reaction of melamine, organic acid and modified graphene. The shell layer has the thickness of 500 nm-5 mu m, the conductivity is good, the spreading performance on the graphite surface is good, the wrapping effect is excellent, in addition, the graphene has flexibility, a space is provided for the electrochemical expansion of silicon, and the structural stability of the material is maintained. The functional structural components are uniformly coated on the surface of the graphite.
As an improvement of the preparation method of the nitrogen-doped carbon-coated silicon composite graphite material, the mass of the shell layer is 5-30% of that of the core layer.
As an improvement of the preparation method of the nitrogen-doped carbon-coated silicon composite graphite material, the modified graphene in the step one is the graphene grafted with-OOH and-OH functional groups, and the modified graphene can react with organic acid and melamine.
As an improvement of the preparation method of the nitrogen-doped carbon-coated silicon composite graphite material, the organic acid in the step one is an organic matter containing-COOH, so that the organic acid can react with melamine and modified graphene under heating to generate functional structural components. And the number of-COOH functional groups is 1 to 5, and the number of carbon atoms is 2 to 20. Preferably, the organic acid is at least one of citric acid, stearic acid and oxalic acid.
As an improvement of the preparation method of the nitrogen-doped carbon-coated silicon composite graphite material, in the step one, the silicon content in the nano-silicon suspension is 5-50%, the particle size of silicon is 30-100 nm, and the liquid in the nano-silicon suspension is at least one of water, ethanol, acetone, isopropanol, n-butanol, tetrahydrofuran and methyl butanone.
As an improvement of the preparation method of the nitrogen-doped carbon-coated silicon composite graphite material, the graphite is at least one of artificial graphite, natural graphite and mesocarbon microbeads.
As an improvement of the preparation method of the nitrogen-doped carbon-coated silicon composite graphite material, the drying temperature in the step one is 60-200 ℃.
As an improvement of the preparation method of the nitrogen-doped carbon-coated silicon composite graphite material, in the first step, the mass ratio of the organic acid, the modified graphene, the melamine, the nano silicon particles and the graphite is (10-30): (0.1-1): (10-30): (0.1-5): 100.
as an improvement of the preparation method of the nitrogen-doped carbon-coated silicon composite graphite material, the rotating speed of the rotary furnace in the second step is 0.1 rpm-1000 rpm; the inert atmosphere comprises at least one of helium, nitrogen, argon and carbon dioxide.
Compared with the prior art, the material prepared by the invention has a core-shell structure, the shell layer is a nitrogen-doped carbon layer embedded with nano-silicon, and the core layer is graphite, wherein the nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after melamine reacts with organic acid and modified graphene. The shell layer obtained by carbonizing the N-C functional component generated by the in-situ reaction of the melamine, the organic acid and the modified graphene has the advantages of good conductivity and good spreadability on the surface of graphite, and the flexibility of the graphene can reserve space for silicon expansion, so that the material provided by the invention has excellent cycle performance and rate capability, and can better meet the requirements of power lithium ion batteries. In addition, the method has simple process and convenient operation, and is suitable for large-scale production and preparation.
Detailed Description
Example 1
The embodiment provides a preparation method of a nitrogen-doped carbon-coated silicon composite graphite material, which at least comprises the following steps:
firstly, 150g of melamine, 200g of citric acid as organic acid, 5g of modified graphene powder and 100g of silicon suspension (ethanol as a solvent) with the solid content of 10% are weighed and placed in a stirring tank, the particle size of silicon is 30-100 nm, the silicon suspension and the silicon suspension are uniformly mixed on a small stirrer, then 1000g D50-15 mu m artificial graphite is weighed and poured into the stirring tank, and after the silicon suspension and the silicon suspension are uniformly stirred, the artificial graphite is transferred and placed into an oven at 80 ℃ for drying. Wherein the modified graphene is graphene grafted with-OOH, -OH functional groups
And step two, drying, grinding, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing N2 for protection at the rotating speed of 800rpm, heating to 300 ℃, preserving heat for 3 hours, reacting amino groups of melamine with carboxyl groups in organic acid and modified graphene respectively to generate functional structural components containing C-N bonds, generating esters by the carboxyl groups of the organic acid and the hydroxyl groups in the modified graphene, and embedding the nano silicon particles into the functional structural components generated in situ after the melamine reacts with the organic acid and the modified graphene. Then the temperature is continuously increased to 800 ℃ for carbonization for 4 h. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the compact nitrogen-doped carbon-coated silicon-carbon composite material of the silicon composite graphite.
The nitrogen-doped carbon-coated silicon composite graphite material obtained in the step two has a core-shell structure, the shell layer is a nitrogen-doped carbon layer embedded with nano silicon, the core layer is graphite, and the nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after melamine reacts with organic acid and modified graphene. The mass of the shell layer is 15% of that of the core layer, and the thickness of the shell layer is 500 nm-5 μm.
Example 2
The embodiment provides a preparation method of a nitrogen-doped carbon-coated silicon composite graphite material, which at least comprises the following steps:
firstly, 250g of melamine, 250g of citric acid as an organic acid, 8g of modified graphene powder and 80g of a silicon suspension (acetone as a solvent) with a solid content of 12% are weighed and placed in a stirring tank, the particle size of silicon is 30-100 nm, the silicon suspension and the silicon suspension are uniformly mixed on a small stirrer, then 1000g D50-10 mu m natural graphite is weighed and poured into the stirring tank, and after the silicon suspension and the silicon suspension are uniformly stirred, the natural graphite is transferred and placed into an oven at 100 ℃ for drying. Wherein the modified graphene is graphene grafted with-OOH, -OH functional groups
And step two, drying, grinding, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing argon at the rotation speed of 600rpm, heating to 400 ℃, keeping the temperature for 4h, reacting amino groups of melamine with carboxyl groups in organic acid and modified graphene respectively to generate functional structural components containing C-N bonds, generating esters by the carboxyl groups of the organic acid and the hydroxyl groups in the modified graphene, and embedding nano silicon particles into the functional structural components generated in situ after the melamine reacts with the organic acid and the modified graphene. Then the temperature is continuously increased to 900 ℃ for carbonization for 5 h. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the compact nitrogen-doped carbon-coated silicon-carbon composite material of the silicon composite graphite.
The nitrogen-doped carbon-coated silicon composite graphite material obtained in the step two has a core-shell structure, the shell layer is a nitrogen-doped carbon layer embedded with nano silicon, the core layer is graphite, and the nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after melamine reacts with organic acid and modified graphene. The mass of the shell layer is 17 percent of the mass of the core layer, and the thickness of the shell layer is 500 nm-5 mu m.
Example 3
The embodiment provides a preparation method of a nitrogen-doped carbon-coated silicon composite graphite material, which at least comprises the following steps:
firstly, 200g of melamine, 180g of stearic acid as organic acid, 4g of modified graphene powder and 50g of silicon suspension (isopropanol as a solvent) with the solid content of 20% are weighed and placed in a stirring tank, the particle size of silicon is 30-100 nm, the silicon suspension and the silicon suspension are uniformly mixed on a small stirrer, then 1000g D50-18 mu m natural graphite is weighed and poured into the stirring tank, and the mixture is transferred and placed into an oven at 150 ℃ for drying after being uniformly stirred. Wherein, the modified graphene is the graphene grafted with-OOH, -OH functional groups.
And step two, drying, grinding, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing argon at the rotation speed of 500rpm, heating to 200 ℃, keeping the temperature for 2 hours, reacting amino groups of melamine with carboxyl groups in organic acid and modified graphene respectively to generate functional structural components containing C-N bonds, generating esters by the carboxyl groups of the organic acid and the hydroxyl groups in the modified graphene, and embedding nano silicon particles into the functional structural components generated in situ after the melamine reacts with the organic acid and the modified graphene. Then the temperature is continuously increased to 700 ℃ for carbonization for 6 h. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the compact nitrogen-doped carbon-coated silicon-carbon composite material of the silicon composite graphite.
The nitrogen-doped carbon-coated silicon composite graphite material obtained in the step two has a core-shell structure, the shell layer is a nitrogen-doped carbon layer embedded with nano silicon, the core layer is graphite, and the nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after melamine reacts with organic acid and modified graphene. The mass of the shell layer is 18 percent of that of the core layer, and the thickness of the shell layer is 500 nm-5 mu m.
Example 4
The embodiment provides a preparation method of a nitrogen-doped carbon-coated silicon composite graphite material, which at least comprises the following steps:
firstly, 120g of melamine, 220g of oxalic acid as organic acid, 7g of modified graphene powder and 100g of 25% solid content silicon suspension (isopropanol as a solvent) are weighed and placed in a stirring tank, the particle size of silicon is 30-100 nm, the silicon suspension and the suspension are uniformly mixed on a small stirrer, then 1000g D50-20 mu m intermediate phase carbon microspheres are weighed and poured into the stirring tank, and after the silicon suspension and the silicon suspension are uniformly stirred, the intermediate phase carbon microspheres are transferred and placed into an oven at 120 ℃ for drying. Wherein, the modified graphene is the graphene grafted with-OOH, -OH functional groups.
And step two, drying, grinding, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing argon for protection at the rotating speed of 300rpm, heating to 250 ℃, keeping the temperature for 2.5h, reacting amino groups of melamine with carboxyl groups in organic acid and modified graphene respectively to generate functional structural components containing C-N bonds, generating esters by the carboxyl groups in the organic acid and the hydroxyl groups in the modified graphene, and embedding the nano silicon particles into the functional structural components generated in situ after the melamine reacts with the organic acid and the modified graphene. Then the temperature is continuously increased to 750 ℃ for carbonization for 10 h. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the compact nitrogen-doped carbon-coated silicon-carbon composite material of the silicon composite graphite.
The nitrogen-doped carbon-coated silicon composite graphite material obtained in the step two has a core-shell structure, the shell layer is a nitrogen-doped carbon layer embedded with nano silicon, the core layer is graphite, and the nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after melamine reacts with organic acid and modified graphene. The mass of the shell layer is 20% of that of the core layer, and the thickness of the shell layer is 500 nm-5 μm.
Example 5
The embodiment provides a preparation method of a nitrogen-doped carbon-coated silicon composite graphite material, which at least comprises the following steps:
firstly, 280g of melamine, 110g of citric acid as organic acid, 8g of modified graphene powder and 90g of silicon suspension (ethanol as a solvent) with the solid content of 16% are weighed and placed in a stirring tank, the particle size of silicon is 30-100 nm, the silicon suspension and the silicon suspension are uniformly mixed on a small stirrer, then 1000g D50-15 mu m artificial graphite is weighed and poured into the stirring tank, and after the silicon suspension and the silicon suspension are uniformly stirred, the artificial graphite is transferred and placed into an oven at 130 ℃ for drying. Wherein the modified graphene is graphene grafted with-OOH, -OH functional groups
And step two, drying, grinding, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing N2 for protection at the rotation speed of 750rpm, heating to 350 ℃, keeping the temperature for 3.5h, reacting amino groups of melamine with carboxyl groups in organic acid and modified graphene respectively to generate functional structural components containing C-N bonds, generating esters by the carboxyl groups in the organic acid and the hydroxyl groups in the modified graphene, and embedding the nano silicon particles into the functional structural components generated in situ after the melamine reacts with the organic acid and the modified graphene. Then the temperature is continuously increased to 850 ℃ for carbonization for 12 h. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the compact nitrogen-doped carbon-coated silicon-carbon composite material of the silicon composite graphite.
The nitrogen-doped carbon-coated silicon composite graphite material obtained in the step two has a core-shell structure, the shell layer is a nitrogen-doped carbon layer embedded with nano silicon, the core layer is graphite, and the nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after melamine reacts with organic acid and modified graphene. The mass of the shell layer is 12 percent of the mass of the core layer, and the thickness of the shell layer is 500 nm-5 mu m.
Example 6
The embodiment provides a preparation method of a nitrogen-doped carbon-coated silicon composite graphite material, which at least comprises the following steps:
firstly, 260g of melamine, 130g of citric acid as organic acid, 5.5g of modified graphene powder and 70g of silicon suspension (water as a solvent) with the solid content of 26% are weighed and placed in a stirring tank, the particle size of silicon is 30-100 nm, the silicon suspension and the silicon suspension are uniformly mixed on a small stirrer, then 1000g D50-35 mu m artificial graphite is weighed and poured into the stirring tank, and after the silicon suspension and the silicon suspension are uniformly stirred, the artificial graphite is transferred and placed into an oven at 140 ℃ for drying. Wherein the modified graphene is graphene grafted with-OOH, -OH functional groups
And step two, drying, grinding, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing argon at the rotation speed of 550rpm, heating to 150 ℃, keeping the temperature for 1.5h, reacting amino groups of melamine with carboxyl groups in organic acid and modified graphene respectively to generate functional structural components containing C-N bonds, generating esters by the carboxyl groups of the organic acid and the hydroxyl groups in the modified graphene, and embedding the nano silicon particles into the functional structural components generated in situ after the melamine reacts with the organic acid and the modified graphene. Then the temperature is continuously increased to 650 ℃ for carbonization for 20 h. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the compact nitrogen-doped carbon-coated silicon-carbon composite material of the silicon composite graphite.
The nitrogen-doped carbon-coated silicon composite graphite material obtained in the step two has a core-shell structure, the shell layer is a nitrogen-doped carbon layer embedded with nano silicon, the core layer is graphite, and the nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after melamine reacts with organic acid and modified graphene. The mass of the shell layer is 10 percent of that of the core layer, and the thickness of the shell layer is 500 nm-5 mu m.
Example 7
The embodiment provides a preparation method of a nitrogen-doped carbon-coated silicon composite graphite material, which at least comprises the following steps:
firstly, 160g of melamine, 230g of citric acid as an organic acid, 4.5g of modified graphene powder and 75g of a silicon suspension (water as a solvent) with a solid content of 21% are weighed and placed in a stirring tank, the particle size of silicon is 30-100 nm, the silicon suspension and the silicon suspension are uniformly mixed on a small stirrer, then 1000g D50-35 μm artificial graphite is weighed and poured into the stirring tank, and after the silicon suspension and the silicon suspension are uniformly stirred, the artificial graphite is transferred and placed into an oven at 180 ℃ for drying. Wherein the modified graphene is graphene grafted with-OOH, -OH functional groups
And step two, drying, grinding, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing argon for protection at the rotating speed of 650rpm, heating to 210 ℃, keeping the temperature for 1.8h, reacting amino groups of melamine with carboxyl groups in organic acid and modified graphene respectively to generate functional structural components containing C-N bonds, generating esters from the carboxyl groups in the organic acid and the hydroxyl groups in the modified graphene, and embedding the nano silicon particles into the functional structural components generated in situ after the reaction of the melamine with the organic acid and the modified graphene. Then the temperature is continuously increased to 720 ℃ for carbonization for 18 h. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the compact nitrogen-doped carbon-coated silicon-carbon composite material of the silicon composite graphite.
The nitrogen-doped carbon-coated silicon composite graphite material obtained in the step two has a core-shell structure, the shell layer is a nitrogen-doped carbon layer embedded with nano silicon, the core layer is graphite, and the nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after melamine reacts with organic acid and modified graphene. The mass of the shell layer is 15% of that of the core layer, and the thickness of the shell layer is 500 nm-5 μm.
Example 8
The embodiment provides a preparation method of a nitrogen-doped carbon-coated silicon composite graphite material, which at least comprises the following steps:
firstly, 155g of melamine, 205g of citric acid as an organic acid, 2.5g of modified graphene powder and 80g of a silicon suspension (ethanol as a solvent) with a solid content of 12% are weighed and placed in a stirring tank, the particle size of silicon is 30-100 nm, the silicon suspension and the silicon suspension are uniformly mixed on a small stirrer, then 1000g D50-15 mu m artificial graphite is weighed and poured into the stirring tank, and after the silicon suspension and the silicon suspension are uniformly stirred, the artificial graphite is transferred and placed into a 160 ℃ oven to be dried. Wherein the modified graphene is graphene grafted with-OOH, -OH functional groups
And step two, drying, grinding, sieving with a 325-mesh sieve, transferring the powder into a cavity of a rotary furnace, introducing argon for protection at the rotation speed of 750rpm, heating to 230 ℃, keeping the temperature for 1.6h, reacting amino groups of melamine with carboxyl groups in organic acid and modified graphene respectively to generate functional structural components containing C-N bonds, generating esters by the carboxyl groups in the organic acid and the hydroxyl groups in the modified graphene, and embedding the nano silicon particles into the functional structural components generated in situ after the reaction of the melamine with the organic acid and the modified graphene. Then the temperature is increased to 780 ℃ continuously for carbonization for 14 h. And after the sample is cooled, taking out the sample, grinding, and screening by a 325-mesh screen to obtain the compact nitrogen-doped carbon-coated silicon-carbon composite material of the silicon composite graphite.
The nitrogen-doped carbon-coated silicon composite graphite material obtained in the step two has a core-shell structure, the shell layer is a nitrogen-doped carbon layer embedded with nano silicon, the core layer is graphite, and the nitrogen-doped carbon layer is obtained by carbonizing functional structure components generated in situ after melamine reacts with organic acid and modified graphene. The mass of the shell layer is 15% of that of the core layer, and the thickness of the shell layer is 500 nm-5 μm.
Comparative example 1
A commercially available silicon-carbon cathode is adopted, the shell layer is carbon, the core layer is silicon, the mass of the shell layer is 10% of that of the core layer, and the thickness of the shell layer is 500 nm-5 mu m.
Electrochemical cycling performance was tested using the following method: the materials prepared in examples 1-8 and the material provided in comparative example 1 were taken and mixed as follows: silicon-carbon composite material: SP: CMC: SBR 94: 2: mixing the raw materials according to a mass ratio of 1.5:2.5, adding a proper amount of purified water serving as a dispersing agent to prepare slurry, coating the slurry on a copper foil, and preparing a negative plate through vacuum drying and rolling; the positive electrode adopts a metal lithium sheet and 1mol/L LiPF is used6The electrolyte mixed by three-component mixed solvent according to EC, DMC and EMC 1: 1(v/v) adopts polyThe propylene microporous membrane is a diaphragm and assembled into a CR2016 type button cell in an inert gas glove box system filled with argon. The charge and discharge test of the button cell is carried out on a Neware cell test system of Shenzhen Newway Limited company, and the charge and discharge voltage is limited to 0.005-1.5V at the constant current of 0.1C under the normal temperature condition.
The samples prepared in each example and comparative example were assembled into button cells, respectively, and then subjected to electrical property tests, wherein the first charge-discharge gram capacity and the first coulombic efficiency are shown in table 1.
Table 1: electricity for button cell comprising materials prepared using the methods of examples 1 to 8 and materials provided in comparative example 1
And (5) performance test results.
Table 2: rate performance test results for button cells using the materials provided in example 1 and comparative example 1.
From tables 1 and 2, it can be seen that: the material prepared by the method has excellent cycle performance and rate capability, and can better meet the requirements of power lithium ion batteries. In addition, the method has simple process and convenient operation, and is suitable for large-scale production and preparation.
Appropriate changes and modifications to the embodiments described above will become apparent to those skilled in the art from the disclosure and teachings of the foregoing description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (9)
1. A preparation method of a nitrogen-doped carbon-coated silicon composite graphite material is characterized by at least comprising the following steps:
step one, melamine is used as a nitrogen source, organic acid is used as a carbon source, modified graphene is used as a conductive bridge, the melamine, the organic acid, the modified graphene and the nano-silicon turbid liquid are uniformly mixed, then graphite is added, and the mixture is uniformly mixed and dried;
step two, grinding and sieving the dried material mixed in the step one, then transferring the material to a rotary furnace, introducing inert atmosphere, heating to 100-500 ℃, preserving heat for 0.1-5 h, and embedding the nano silicon particles into functional structure components generated in situ after reaction of melamine, organic acid and modified graphene; then, continuously heating to 500-1000 ℃, carbonizing for 0.5-24 h, cooling, scattering and sieving to obtain a compact nitrogen-doped carbon-coated silicon composite graphite material;
the nitrogen-doped carbon-coated silicon composite graphite material obtained in the step two has a core-shell structure, wherein a shell layer is a nitrogen-doped carbon layer embedded with nano silicon, a core layer is graphite, and the nitrogen-doped carbon layer is obtained by carbonizing a functional structure component generated in situ after the reaction of melamine, organic acid and modified graphene;
the organic acid is at least one of citric acid, stearic acid and oxalic acid.
2. The method for preparing the nitrogen-doped carbon-coated silicon composite graphite material as claimed in claim 1, wherein the mass of the shell layer is 5-30% of the mass of the core layer.
3. The method according to claim 1, wherein the modified graphene obtained in the first step is a graphene grafted with-COOH, -OH functional groups.
4. The method for preparing the nitrogen-doped carbon-coated silicon composite graphite material according to claim 1, wherein the organic acid in the step one is an organic substance containing-COOH, the number of-COOH functional groups is 1 to 5, and the number of carbon atoms is 2 to 20.
5. The method for preparing the nitrogen-doped carbon-coated silicon composite graphite material as claimed in claim 1, wherein the silicon content in the nano-silicon suspension in the step one is 5-50%, the particle size of silicon is 30-100 nm, and the liquid in the nano-silicon suspension is at least one of water, ethanol, acetone, isopropanol, n-butanol, tetrahydrofuran and methyl butanone.
6. The method of claim 1, wherein the graphite in the step one is at least one of artificial graphite, natural graphite and mesocarbon microbeads.
7. The method for preparing nitrogen-doped carbon-coated silicon composite graphite material according to claim 1, wherein the drying temperature in the first step is 60-200 ℃.
8. The method for preparing the nitrogen-doped carbon-coated silicon composite graphite material according to claim 1, wherein in the first step, the mass ratio of the organic acid to the modified graphene to the melamine to the nano-silicon particles to the graphite is (10-30): (0.1-1): (10-30): (0.1-5): 100.
9. the method for preparing the nitrogen-doped carbon-coated silicon composite graphite material according to claim 1, wherein the rotation speed of the rotary furnace in the second step is 0.1rpm to 1000 rpm; the inert atmosphere comprises at least one of helium, nitrogen, argon and carbon dioxide.
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