CN107403919B - Composite material of nitrogen-doped carbon material coated with silicon monoxide and preparation method thereof - Google Patents
Composite material of nitrogen-doped carbon material coated with silicon monoxide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a composite material of nitrogen-doped carbon material coated with silicon oxide, which takes the silicon oxide as a core and the nitrogen-doped carbon material coated with the silicon oxide to form a core-shell structure, wherein the nitrogen-doped carbon material is a mixture of nitrogen-doped graphene and nitrogen-doped oxidized asphalt; the composite material of the nitrogen-doped carbon material coated with the silicon oxide comprises the following components in percentage by weight: 70-90% of silicon monoxide, 5-20% of nitrogen-doped graphene and 3-15% of nitrogen-doped asphalt oxide; the invention also discloses a preparation method of the composite material of the nitrogen-doped carbon material coated with the silicon monoxide. According to the invention, the silicon oxide is used as the core, and the nitrogen-doped carbon material is used for coating the silicon oxide to form the core-shell structure, so that the electronic conductivity of the negative electrode material is improved, the volume change of the negative electrode material in the lithium desorption and insertion process can be buffered, the structural stability of the material in the circulating process is improved, and the advantages of high reversible capacity and good circulating performance are achieved.
Description
Technical Field
The invention relates to the technical field of a silicon oxide composite negative electrode material, in particular to a nitrogen-doped carbon material coated silicon oxide composite material and a preparation method thereof.
Background
Lithium ion batteries have high specific energy, long cycle life, and the like, and are widely used in the fields of portable electronic devices, computers, and the like. The lithium ion battery mainly comprises four major parts, namely a positive electrode material, a negative electrode material, a diaphragm and electrolyte, wherein the negative electrode material of the commercial lithium ion battery is mainly a graphite negative electrode material, but the theoretical capacity of the lithium ion battery is only 372mAh/g, and the requirement of people on the high-energy-density battery cannot be met. Therefore, the development of a negative electrode material having a high specific capacity, a high charge/discharge efficiency, and a good cycle stability has become an important problem to be solved.
The silicon negative electrode material has the advantages of high theoretical capacity (4200mAh/g), low lithium intercalation/deintercalation platform, abundant resources, good safety and the like, and is one of the most potential lithium ion battery negative electrode materials at present. However, during the charging and discharging processes, the silicon negative electrode material is accompanied with huge volume change (400%), which causes pulverization of the silicon active material and cracking of the click coating, and finally causes rapid capacity attenuation, thus seriously hindering the practical application of the silicon negative electrode material in the lithium ion battery. Meanwhile, since silicon is a semiconductor material, intrinsic conductivity is poor (6.7 × 10)-4s/cm) resulting in poor rate capability of the silicon material. The silicon oxide has the advantages of high theoretical specific capacity (2600mAh/g), good safety, low price and the like, but has some problems, such as the change of the volume of nearly 200% in the lithium desorption process, click pulverization, damage to a conductive network and rapid capacity attenuation; inert lithium oxide and lithium silicate phases can be generated in the process of lithium intercalation for the first time, so that the coulomb efficiency of the first cycle is low; in the subsequent charge and discharge processes, Li is consumed due to the continuous generation of SEI film at the interface of solid electrolyte phase+The coulombic efficiency is lower than 100%, so that the lithium-removable capacity of the battery cathode relative to the anode is greatly reduced; SiO, as a semiconductor, has much lower electrical conductivity than graphite, and therefore, has severe polarization during large current charging and discharging. SiO has a lower theoretical capacity than silicon, but the strength of the Si-O bond is 2 times that of the Si-Si bond, and Li is generated during the first-week reaction2The O compound has a buffering effect on volume expansion, and thus the cycle performance thereof is much superior to that of silicon, and has attracted much attention of many researchers.
In response to the defects of the silicon oxide, researchers propose to compound SiO with other conductive materials such as carbon materials. Graphene as a novel carbon nanomaterial consisting of a single layer of sp2Compact carbon atomThe materials are stacked into a two-dimensional honeycomb structure, have the advantages of high electronic conductivity, good flexibility, high mechanical strength and the like, can better buffer the volume effect and improve the electronic channel, determine the great application potential in the field of lithium ion batteries by the characteristics, and are increasingly researched for preparing cathode materials by using the composite silicon oxide. However, since graphene has no band gap, the conductivity of graphene cannot be completely controlled like that of a conventional semiconductor, and graphene has a smooth and inert surface, and is not easily compounded with other materials, thereby hindering the application of graphene. Therefore, the development of a negative electrode material of a carbon material composite silicon oxide lithium battery with good comprehensive performance is one of the problems to be solved urgently in the field.
Disclosure of Invention
The invention provides a composite material of a nitrogen-doped carbon material coated with silicon monoxide and a preparation method thereof, which can improve the electronic conductivity of a negative electrode material, buffer the volume change of the negative electrode material in the lithium desorption and insertion process, improve the structural stability of the material in the circulation process, and have the advantages of high reversible capacity and good circulation performance.
The composite material with the nitrous oxide coated by the nitrogen-doped carbon material provided by the invention takes the nitrous oxide as a core, and the nitrous oxide is coated by the nitrogen-doped carbon material to form a core-shell structure, wherein the nitrogen-doped carbon material is a mixture of nitrogen-doped graphene and nitrogen-doped oxidized asphalt; the composite material of the nitrogen-doped carbon material coated with the silicon oxide comprises the following components in percentage by weight: 70-90% of silicon monoxide, 5-20% of nitrogen-doped graphene and 3-15% of nitrogen-doped asphalt oxide.
In specific embodiments, the weight percentage of the silicon oxide in the composite material in which the nitrogen-doped carbon material coats the silicon oxide can be 75%, 78%, 80%, 82%, 85%, 89%; the weight percentage of the nitrogen-doped graphene in the composite material of the nitrogen-doped carbon material coated with the silicon oxide can be 7%, 10%, 13%, 15% and 18%; the weight percentage of the nitrogen-doped oxidized asphalt in the composite material of the nitrogen-doped carbon material coated with the silicon oxide can be 5%, 7%, 9%, 10%, 12% and 14%.
Preferably, the nitrogen content in the composite material of the nitrogen-doped carbon material coated with the silicon oxide is 3-15 wt%.
Preferably, in the composite material of the nitrogen-doped carbon material coated with the silicon oxide, the particle size D50 of the silicon oxide is 4-9 μm.
The invention provides a preparation method of a nitrogen-doped carbon material coated with a silicon monoxide composite material, which comprises the following steps:
s1, preparing graphene oxide: adding water to graphite for dispersion, adding concentrated sulfuric acid for ball milling, then adding a mixed solution of benzoyl peroxide and hydrogen peroxide, continuing ball milling to obtain graphene oxide slurry, and centrifuging, washing and drying the graphene oxide slurry to obtain graphene oxide powder;
s2, preparation of oxidized asphalt: uniformly mixing asphalt, ethanol and an oxidant, heating and stirring to obtain oxidized asphalt slurry, centrifuging, washing and drying the oxidized asphalt slurry to obtain oxidized asphalt powder;
s3, mechanical mixing: the preparation method comprises the steps of dispersing graphene oxide powder and asphalt oxide powder by using ethanol as a dispersing agent to obtain a composite slurry, uniformly mixing silicon oxide and ethanol, adding the composite slurry, then adding melamine, dispersing and stirring at a high speed for 5-24 hours to obtain a mixed material, volatilizing the mixed material by using a solvent, and drying to obtain the melamine/graphene oxide/asphalt oxide coated silicon oxide composite powder.
S4, high-temperature pyrolysis: and (3) putting the melamine/graphene oxide/asphalt oxide coated silicon monoxide composite powder into a pyrolysis device, introducing ammonia gas into the pyrolysis device, heating to 400-800 ℃, keeping nitrogen continuously introduced, carrying out heat preservation reaction, and cooling to obtain the nitrogen-doped carbon material coated silicon monoxide composite material.
Preferably, in S1, the particle size of the graphite is 50-400 μm; preferably, in S1, the graphite is flake graphite and/or expanded graphite.
Preferably, in S1, the weight ratio of benzoyl peroxide to hydrogen peroxide in the mixed solution is 1: 1.
preferably, in S1, the weight ratio of graphite, concentrated sulfuric acid, and the mixed solution is 1: 2-6: 1 to 4.
Preferably, in the step S1, concentrated sulfuric acid is added to perform ball milling for 3-10 hours, then mixed liquid of benzoyl peroxide and hydrogen peroxide is added, and ball milling is continued for 5-48 hours to obtain graphene oxide slurry.
The ball milling is carried out in a ceramic ball milling tank.
Preferably, in S2, the weight ratio of bitumen to oxidant is 1: 0.5 to 3.
Preferably, in S2, the asphalt is one or a mixture of more than two of coal asphalt, petroleum asphalt and natural asphalt.
Preferably, in S2, the oxidizing agent is one or a mixture of two or more of hydrogen peroxide, benzoyl peroxide and concentrated sulfuric acid.
Preferably, in S2, the heating and stirring temperature is 50-80 ℃, and the heating and stirring time is 2-7 hours.
Preferably, in S3, the weight ratio of the silica to the melamine is 1: 0.1 to 1.5.
Preferably, in S3, the drying temperature is 75-85 ℃ and the drying time is 10-14 h.
In the invention, high-speed dispersion is performed using a high-speed disperser.
Preferably, in S4, the ammonia gas is introduced for 10min at a flow rate of 200 mL/min.
Preferably, in S4, the reaction time is kept at 1-10 h.
In the present invention, the cooling method is natural cooling.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, nitrogen-containing functional groups are introduced into the carbon material, so that the surface polarity of the carbon material is increased, the wettability of the carbon material is improved, and the diffusion resistance of electrolyte ions in pores is reduced.
2. The invention adopts solid melamine and gaseous ammonia dual nitrogen source, and can adjust the nitrogen content in a wider range.
3. The invention can improve the electronic conductivity of the cathode material, buffer the volume change of the cathode material in the process of lithium desorption and intercalation, improve the structural stability of the material in the circulating process, and has the advantages of high reversible capacity and good circulating performance.
Drawings
FIG. 1 is a scanning electron microscope image of the composite material of the nitrogen-doped carbon material coated with silica prepared in example 1 at a magnification of 5000 times;
FIG. 2 is a scanning electron microscope image of the composite material of the nitrogen-doped carbon material coated with silica prepared in example 1 at a magnification of 10000 times;
FIG. 3 is a graph showing the distribution of particle sizes of the composite material of the nitrous oxide coated with the nitrogen-doped carbon material prepared in example 1;
FIG. 4 is an XPS spectrum of the composite material with the nitrous oxide coated with the nitrogen-doped carbon material prepared in example 1.
Detailed Description
The composite material with the nitrous oxide coated by the nitrogen-doped carbon material provided by the invention takes the nitrous oxide as a core, and the nitrous oxide is coated by the nitrogen-doped carbon material to form a core-shell structure, wherein the nitrogen-doped carbon material is a mixture of nitrogen-doped graphene and nitrogen-doped oxidized asphalt; the composite material of the nitrogen-doped carbon material coated with the silicon oxide comprises the following components in percentage by weight: 70-90% of silicon monoxide, 5-20% of nitrogen-doped graphene and 3-15% of nitrogen-doped asphalt oxide.
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A composite material with a nitrogen-doped carbon material coated with silicon oxide takes silicon oxide as a core, and the nitrogen-doped carbon material is coated with the silicon oxide to form a core-shell structure, wherein the nitrogen-doped carbon material is a mixture of nitrogen-doped graphene and nitrogen-doped pitch oxide; the composite material of the nitrogen-doped carbon material coated with the silicon oxide comprises the following components in percentage by weight: 70% of silicon monoxide, 20% of nitrogen-doped graphene and 10% of nitrogen-doped asphalt oxide;
wherein, in the composite material of the nitrogen-doped carbon material coated with the silicon oxide, the nitrogen content is 7 wt%, and the particle size D50 of the silicon oxide is 4.20 μm;
the composite material of the nitrogen-doped carbon material coated with the silicon monoxide is prepared by the following steps:
s1, preparing graphene oxide: putting crystalline flake graphite with the particle size of 50-400 microns into a ceramic ball milling tank, adding water for dispersing, adding concentrated sulfuric acid for ball milling for 5 hours, then adding a mixed solution of benzoyl peroxide and hydrogen peroxide, continuing ball milling for 20 hours to obtain graphene oxide slurry, and centrifuging, washing and drying the graphene oxide slurry to obtain graphene oxide powder; wherein the weight ratio of the benzoyl peroxide to the hydrogen peroxide in the mixed solution is 1:1, the weight ratio of graphite, concentrated sulfuric acid and mixed liquid is 1: 2: 2;
s2, preparation of oxidized asphalt: adding coal tar pitch, ethanol and an oxidant into a three-neck flask, uniformly mixing, heating and stirring at 50 ℃ for 2 hours to obtain oxidized asphalt slurry, centrifuging, washing and drying the oxidized asphalt slurry to obtain oxidized asphalt powder; wherein the weight ratio of the coal pitch to the oxidant is 1: 0.7; the oxidant is hydrogen peroxide;
s3, mechanical mixing: dispersing graphene oxide powder and asphalt oxide powder in a high-speed dispersion machine by taking ethanol as a dispersing agent to obtain composite slurry, uniformly mixing silicon monoxide and ethanol, adding the composite slurry, then adding melamine, dispersing and stirring at a high speed for 15 hours to obtain a mixed material, volatilizing a solvent for the mixed material, and drying at 80 ℃ for 12 hours to obtain melamine/graphene oxide/asphalt oxide coated silicon monoxide composite powder; wherein the weight ratio of the silicon monoxide to the melamine is 1: 0.8.
s4, high-temperature pyrolysis: adding the melamine/graphene oxide/asphalt oxide coated silicon monoxide composite powder into a porcelain boat, transferring the porcelain boat to the middle of a tube furnace, introducing ammonia gas with the flow rate of 200mL/min for 10min, heating to 400 ℃, keeping nitrogen gas continuously introduced, carrying out heat preservation reaction for 2h, and naturally cooling to obtain the nitrogen-doped carbon material coated silicon monoxide composite material.
The scanning electron microscope image at 5000 magnification, the scanning electron microscope image at 10000 magnification, the particle size distribution diagram and the XPS energy spectrum diagram of the composite material in which the nitrogen-doped carbon material prepared in example 1 is coated with the silicon monoxide are respectively shown in fig. 1, fig. 2, fig. 3 and fig. 4. As can be seen from FIG. 1, the particle size of the composite material of the nitrous oxide coated by the nitrogen-doped carbon material prepared in example 1 is small and is in a random granular shape; the graphene structure is clearly seen in fig. 2, and the particle size distribution of the composite material in which the nitrogen-doped carbon material coats the silicon monoxide in fig. 3 corresponds to the scanning electron microscope images shown in fig. 1 and 2; it can be seen from fig. 4 that the composite material in which the nitrous oxide is coated with the nitrogen-doped carbon material contains more nitrogen and carbon elements.
Example 2
A composite material with a nitrogen-doped carbon material coated with silicon oxide takes silicon oxide as a core, and the nitrogen-doped carbon material is coated with the silicon oxide to form a core-shell structure, wherein the nitrogen-doped carbon material is a mixture of nitrogen-doped graphene and nitrogen-doped pitch oxide; the composite material of the nitrogen-doped carbon material coated with the silicon oxide comprises the following components in percentage by weight: 80% of silicon monoxide, 10% of nitrogen-doped graphene and 10% of nitrogen-doped asphalt oxide;
wherein, in the composite material of the nitrogen-doped carbon material coated with the silicon oxide, the nitrogen content is 12 wt%, and the particle size D50 of the silicon oxide is 6.50 μm;
the composite material of the nitrogen-doped carbon material coated with the silicon monoxide is prepared by the following steps:
s1, preparing graphene oxide: putting crystalline flake graphite with the particle size of 50-300 microns into a ceramic ball milling tank, adding water for dispersing, adding concentrated sulfuric acid for ball milling for 3 hours, then adding a mixed solution of benzoyl peroxide and hydrogen peroxide, continuing ball milling for 28 hours to obtain graphene oxide slurry, and centrifuging, washing and drying the graphene oxide slurry to obtain graphene oxide powder; wherein the weight ratio of the benzoyl peroxide to the hydrogen peroxide in the mixed solution is 1:1, the weight ratio of graphite, concentrated sulfuric acid and mixed liquid is 1: 4: 3;
s2, preparation of oxidized asphalt: adding petroleum asphalt, ethanol and an oxidant into a three-neck flask, uniformly mixing, heating and stirring at 80 ℃ for 5 hours to obtain oxidized asphalt slurry, and centrifuging, washing and drying the oxidized asphalt slurry to obtain oxidized asphalt powder; wherein the weight ratio of the petroleum asphalt to the oxidant is 1: 1.7, the oxidant is concentrated sulfuric acid;
s3, mechanical mixing: dispersing graphene oxide powder and asphalt oxide powder in a high-speed dispersion machine by taking ethanol as a dispersing agent to obtain composite slurry, uniformly mixing silicon monoxide and ethanol, adding the composite slurry, then adding melamine, dispersing and stirring at a high speed for 10 hours to obtain a mixed material, volatilizing a solvent for the mixed material, and drying at 85 ℃ for 12 hours to obtain melamine/graphene oxide/asphalt oxide coated silicon monoxide composite powder; wherein the weight ratio of the silicon monoxide to the melamine is 1: 1.1.
s4, high-temperature pyrolysis: adding the melamine/graphene oxide/asphalt oxide coated silicon monoxide composite powder into a porcelain boat, transferring the porcelain boat to the middle of a tube furnace, introducing ammonia gas with the flow rate of 200mL/min for 10min, heating to 450 ℃, keeping nitrogen gas continuously introduced, carrying out heat preservation reaction for 7h, and naturally cooling to obtain the nitrogen-doped carbon material coated silicon monoxide composite material.
Example 3
A composite material with a nitrogen-doped carbon material coated with silicon oxide takes silicon oxide as a core, and the nitrogen-doped carbon material is coated with the silicon oxide to form a core-shell structure, wherein the nitrogen-doped carbon material is a mixture of nitrogen-doped graphene and nitrogen-doped pitch oxide; the composite material of the nitrogen-doped carbon material coated with the silicon oxide comprises the following components in percentage by weight: 85% of silicon monoxide, 10% of nitrogen-doped graphene and 5% of nitrogen-doped asphalt oxide;
wherein, in the composite material of the nitrogen-doped carbon material coated with the silicon oxide, the nitrogen content is 12 wt%, and the particle size D50 of the silicon oxide is 8.50 μm;
the composite material of the nitrogen-doped carbon material coated with the silicon monoxide is prepared by the following steps:
s1, preparing graphene oxide: putting expanded graphite with the particle size of 50-300 microns into a ceramic ball milling tank, dispersing the expanded graphite in water, adding concentrated sulfuric acid to perform ball milling for 10 hours, then adding a mixed solution of benzoyl peroxide and hydrogen peroxide, continuing ball milling for 15 hours to obtain graphene oxide slurry, and centrifuging, washing and drying the graphene oxide slurry to obtain graphene oxide powder; wherein the weight ratio of the benzoyl peroxide to the hydrogen peroxide in the mixed solution is 1:1, the weight ratio of graphite, concentrated sulfuric acid and mixed liquid is 1: 2.5: 3;
s2, preparation of oxidized asphalt: adding natural asphalt, ethanol and an oxidant into a three-neck flask, uniformly mixing, heating and stirring at 60 ℃ for 3 hours to obtain oxidized asphalt slurry, centrifuging, washing and drying the oxidized asphalt slurry to obtain oxidized asphalt powder; wherein the weight ratio of the natural asphalt to the oxidant is 1: 1.2, the oxidant is concentrated sulfuric acid;
s3, mechanical mixing: dispersing graphene oxide powder and asphalt oxide powder in a high-speed dispersion machine by taking ethanol as a dispersing agent to obtain composite slurry, uniformly mixing silicon monoxide and ethanol, adding the composite slurry, then adding melamine, dispersing and stirring at a high speed for 18 hours to obtain a mixed material, volatilizing a solvent for the mixed material, and drying at 75 ℃ for 14 hours to obtain melamine/graphene oxide/asphalt oxide coated silicon monoxide composite powder; wherein the weight ratio of the silicon monoxide to the melamine is 1: 0.1.
s4, high-temperature pyrolysis: adding the melamine/graphene oxide/asphalt oxide coated silicon monoxide composite powder into a porcelain boat, transferring the porcelain boat to the middle of a tube furnace, introducing ammonia gas with the flow rate of 200mL/min for 10min, heating to 650 ℃, keeping nitrogen gas continuously introduced, carrying out heat preservation reaction for 3h, and naturally cooling to obtain the nitrogen-doped carbon material coated silicon monoxide composite material.
Example 4
A composite material with a nitrogen-doped carbon material coated with silicon oxide takes silicon oxide as a core, and the nitrogen-doped carbon material is coated with the silicon oxide to form a core-shell structure, wherein the nitrogen-doped carbon material is a mixture of nitrogen-doped graphene and nitrogen-doped pitch oxide; the composite material of the nitrogen-doped carbon material coated with the silicon oxide comprises the following components in percentage by weight: 90% of silicon monoxide, 6% of nitrogen-doped graphene and 4% of nitrogen-doped asphalt oxide;
wherein, in the composite material of the nitrogen-doped carbon material coated with the silicon oxide, the nitrogen content is 13 wt%, and the particle size D50 of the silicon oxide is 7.65 μm;
the composite material of the nitrogen-doped carbon material coated with the silicon monoxide is prepared by the following steps:
s1, preparing graphene oxide: putting expanded graphite with the particle size of 50-300 microns into a ceramic ball milling tank, adding water for dispersing, adding concentrated sulfuric acid for ball milling for 5 hours, then adding a mixed solution of benzoyl peroxide and hydrogen peroxide, continuing ball milling for 30 hours to obtain graphene oxide slurry, and centrifuging, washing and drying the graphene oxide slurry to obtain graphene oxide powder; wherein the weight ratio of the benzoyl peroxide to the hydrogen peroxide in the mixed solution is 1:1, the weight ratio of graphite, concentrated sulfuric acid and mixed liquid is 1: 2.5: 4;
s2, preparation of oxidized asphalt: adding natural asphalt, ethanol and an oxidant into a three-neck flask, uniformly mixing, heating and stirring at 50 ℃ for 7 hours to obtain oxidized asphalt slurry, centrifuging, washing and drying the oxidized asphalt slurry to obtain oxidized asphalt powder; wherein the weight ratio of the natural asphalt to the oxidant is 1: 2.2, the oxidant is benzoyl peroxide;
s3, mechanical mixing: dispersing graphene oxide powder and asphalt oxide powder in a high-speed dispersion machine by taking ethanol as a dispersing agent to obtain composite slurry, uniformly mixing silicon oxide and ethanol, adding the composite slurry, then adding melamine, dispersing and stirring at a high speed for 10 hours to obtain a mixed material, volatilizing the mixed material by using a solvent, and drying at 80 ℃ for 14 hours to obtain melamine/graphene oxide/asphalt oxide coated silicon oxide composite powder; wherein the weight ratio of the silicon monoxide to the melamine is 1: 0.1.
s4, high-temperature pyrolysis: adding the melamine/graphene oxide/asphalt oxide coated silicon monoxide composite powder into a porcelain boat, transferring the porcelain boat to the middle of a tube furnace, introducing ammonia gas with the flow rate of 200mL/min for 10min, heating to 700 ℃, keeping nitrogen gas continuously introduced, carrying out heat preservation reaction for 6h, and naturally cooling to obtain the nitrogen-doped carbon material coated silicon monoxide composite material.
Example 5
A composite material with a nitrogen-doped carbon material coated with silicon oxide takes silicon oxide as a core, and the nitrogen-doped carbon material is coated with the silicon oxide to form a core-shell structure, wherein the nitrogen-doped carbon material is a mixture of nitrogen-doped graphene and nitrogen-doped pitch oxide; the composite material of the nitrogen-doped carbon material coated with the silicon oxide comprises the following components in percentage by weight: 80% of silicon monoxide, 5% of nitrogen-doped graphene and 15% of nitrogen-doped asphalt oxide;
wherein, in the composite material of the nitrogen-doped carbon material coated with the silicon oxide, the nitrogen content is 3 wt%, and the particle size D50 of the silicon oxide is 9.00 mu m;
the composite material of the nitrogen-doped carbon material coated with the silicon monoxide is prepared by the following steps:
s1, preparing graphene oxide: putting expanded graphite with the particle size of 100-300 microns into a ceramic ball milling tank, adding water for dispersing, adding concentrated sulfuric acid for ball milling for 3 hours, then adding a mixed solution of benzoyl peroxide and hydrogen peroxide, continuing ball milling for 48 hours to obtain graphene oxide slurry, and centrifuging, washing and drying the graphene oxide slurry to obtain graphene oxide powder; wherein the weight ratio of the benzoyl peroxide to the hydrogen peroxide in the mixed solution is 1:1, the weight ratio of graphite, concentrated sulfuric acid and mixed liquid is 1: 2: 4;
s2, preparation of oxidized asphalt: adding natural asphalt, ethanol and an oxidant into a three-neck flask, uniformly mixing, heating and stirring at 55 ℃ for 3 hours to obtain oxidized asphalt slurry, centrifuging, washing and drying the oxidized asphalt slurry to obtain oxidized asphalt powder; wherein the weight ratio of the natural asphalt to the oxidant is 1: 0.5, the oxidant is benzoyl peroxide;
s3, mechanical mixing: dispersing graphene oxide powder and asphalt oxide powder in a high-speed dispersion machine by taking ethanol as a dispersing agent to obtain composite slurry, uniformly mixing silicon monoxide and ethanol, adding the composite slurry, then adding melamine, dispersing and stirring at a high speed for 10 hours to obtain a mixed material, volatilizing a solvent for the mixed material, and drying at 75 ℃ for 14 hours to obtain melamine/graphene oxide/asphalt oxide coated silicon monoxide composite powder; wherein the weight ratio of the silicon monoxide to the melamine is 1: 1.5.
s4, high-temperature pyrolysis: adding the melamine/graphene oxide/asphalt oxide coated silicon monoxide composite powder into a porcelain boat, transferring the porcelain boat to the middle of a tube furnace, introducing ammonia gas with the flow rate of 200mL/min for 10min, heating to 800 ℃, keeping nitrogen gas continuously introduced, carrying out heat preservation reaction for 1h, and naturally cooling to obtain the nitrogen-doped carbon material coated silicon monoxide composite material.
Example 6
A composite material with a nitrogen-doped carbon material coated with silicon oxide takes silicon oxide as a core, and the nitrogen-doped carbon material is coated with the silicon oxide to form a core-shell structure, wherein the nitrogen-doped carbon material is a mixture of nitrogen-doped graphene and nitrogen-doped pitch oxide; the composite material of the nitrogen-doped carbon material coated with the silicon oxide comprises the following components in percentage by weight: 80% of silicon monoxide, 17% of nitrogen-doped graphene and 3% of nitrogen-doped asphalt oxide;
wherein, in the composite material of the nitrogen-doped carbon material coated with the silicon oxide, the nitrogen content is 15 wt%, and the particle size D50 of the silicon oxide is 4.00 mu m;
the composite material of the nitrogen-doped carbon material coated with the silicon monoxide is prepared by the following steps:
s1, preparing graphene oxide: putting expanded graphite with the particle size of 100-350 microns into a ceramic ball milling tank, dispersing the expanded graphite in water, adding concentrated sulfuric acid to perform ball milling for 10 hours, then adding a mixed solution of benzoyl peroxide and hydrogen peroxide, continuing ball milling for 5 hours to obtain graphene oxide slurry, and centrifuging, washing and drying the graphene oxide slurry to obtain graphene oxide powder; wherein the weight ratio of the benzoyl peroxide to the hydrogen peroxide in the mixed solution is 1:1, the weight ratio of graphite, concentrated sulfuric acid and mixed liquid is 1: 6: 2;
s2, preparation of oxidized asphalt: adding natural asphalt, ethanol and an oxidant into a three-neck flask, uniformly mixing, heating and stirring at 75 ℃ for 5 hours to obtain oxidized asphalt slurry, centrifuging, washing and drying the oxidized asphalt slurry to obtain oxidized asphalt powder; wherein the weight ratio of the natural asphalt to the oxidant is 1: 3, the oxidant is benzoyl peroxide;
s3, mechanical mixing: dispersing graphene oxide powder and asphalt oxide powder in a high-speed dispersion machine by taking ethanol as a dispersing agent to obtain composite slurry, uniformly mixing silicon monoxide and ethanol, adding the composite slurry, then adding melamine, dispersing and stirring at a high speed for 10 hours to obtain a mixed material, volatilizing a solvent for the mixed material, and drying at 78 ℃ for 11 hours to obtain melamine/graphene oxide/asphalt oxide coated silicon monoxide composite powder; wherein the weight ratio of the silicon monoxide to the melamine is 1: 0.1.
s4, high-temperature pyrolysis: adding the melamine/graphene oxide/asphalt oxide coated silicon monoxide composite powder into a porcelain boat, transferring the porcelain boat to the middle of a tube furnace, introducing ammonia gas with the flow rate of 200mL/min for 10min, heating to 400 ℃, keeping nitrogen gas continuously introduced, carrying out heat preservation reaction for 10h, and naturally cooling to obtain the nitrogen-doped carbon material coated silicon monoxide composite material.
The composite material of the nitrogen-doped carbon material coated with the silicon monoxide prepared in the examples 1 to 6, the superconducting carbon black and the LA133 are mixed according to the mass ratio of 8:1:1, deionized water is used as a solvent to prepare slurry, the slurry is uniformly coated on a copper foil with the thickness of 16 microns, the copper foil is placed into a vacuum oven with the temperature of 90 ℃ for drying for 12 hours, and the copper foil is rolled and then punched into a pole piece. Lithium sheet as counter electrode and LiPF6LiPF with concentration of 1mol/L6Adopting a solution of/EC + PC + DMC (1:1: 1; vt%) as an electrolyte, adopting a Celgard2400 diaphragm, assembling a CR2025 type button cell in an argon glove box, immediately sealing the cell by using a sealing machine, standing for 24 hours, then adopting a Xinwei tester to carry out electrochemical performance test, wherein the charge-discharge cut-off voltage is 5 mV-1.5V (vs Li)+Li), the ambient temperature is 25 +/-2 ℃, and the charge-discharge cycle performance test is as follows: the current density is 100mA/g in 20 weeks and 400mA/g in 21-100 weeks before the test.
The test results of examples 1 to 6 were compared with those of the control group in which the conditions were the same as those of examples 1 to 4 except that the composite material in which the nitrous oxide was coated with the nitrogen-doped carbon material was replaced with the nitrous oxide, and the test results are shown in the following table:
the test data show that the first coulombic efficiency of the button cell is remarkably improved, the first coulombic maximum efficiency can reach 85.2 percent and is improved by 111.9 percent compared with a control group, higher reversible capacity can be maintained after circulation for 100 weeks, the reversible capacity retention rate exceeds 80 percent, and the highest reversible capacity retention rate reaches 90.3 percent, which indicates that the button cell has higher reverse capacity and good cycle performance.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (16)
1. The composite material is characterized in that the silicon oxide is used as a core, and the nitrogen-doped carbon material is used for coating the silicon oxide to form a core-shell structure, wherein the nitrogen-doped carbon material is a mixture of nitrogen-doped graphene and nitrogen-doped oxidized asphalt; the composite material of the nitrogen-doped carbon material coated with the silicon oxide comprises the following components in percentage by weight: 70-90% of silicon monoxide, 5-20% of nitrogen-doped graphene and 3-15% of nitrogen-doped asphalt oxide;
the preparation method of the composite material of the nitrogen-doped carbon material coated with the silicon oxide comprises the following steps:
s1, preparing graphene oxide: adding water to graphite for dispersion, adding concentrated sulfuric acid for ball milling, then adding a mixed solution of benzoyl peroxide and hydrogen peroxide, continuing ball milling to obtain graphene oxide slurry, and centrifuging, washing and drying the graphene oxide slurry to obtain graphene oxide powder;
s2, preparation of oxidized asphalt: uniformly mixing asphalt, ethanol and an oxidant, heating and stirring to obtain oxidized asphalt slurry, centrifuging, washing and drying the oxidized asphalt slurry to obtain oxidized asphalt powder;
s3, mechanical mixing: dispersing graphene oxide powder and asphalt oxide powder by taking ethanol as a dispersing agent to obtain a composite slurry, uniformly mixing silicon oxide and ethanol, adding the composite slurry, then adding melamine, dispersing and stirring at a high speed for 5-24 hours to obtain a mixed material, volatilizing the mixed material by a solvent, and drying to obtain melamine/graphene oxide/asphalt oxide coated silicon oxide composite powder;
s4, high-temperature pyrolysis: and (3) putting the melamine/graphene oxide/asphalt oxide coated silicon monoxide composite powder into a pyrolysis device, introducing ammonia gas into the pyrolysis device, heating to 400-800 ℃, keeping nitrogen continuously introduced, carrying out heat preservation reaction, and cooling to obtain the nitrogen-doped carbon material coated silicon monoxide composite material.
2. The silicon oxide-coated carbon nitride-doped carbon material composite material according to claim 1, wherein the amount of nitrogen doped in the silicon oxide-coated carbon nitride-doped carbon material composite material is 3 to 15 wt%.
3. The composite material of claim 1 or 2, wherein the particle size D50 of the silicon oxide in the composite material of the nitrogen-doped carbon material coated with the silicon oxide is 4-9 μm.
4. The nitrogen-doped carbon material-coated silica composite material according to claim 1, wherein in S1, the particle size of graphite is 50 to 400 μm.
5. The nitrogen-doped carbon material-coated silica composite material according to claim 1, wherein in S1, the graphite is flake graphite and/or expanded graphite.
6. The composite material of the nitrogen-doped carbon material coated with the silicon monoxide as claimed in claim 1 or 4, wherein in S1, the weight ratio of the benzoyl peroxide to the hydrogen peroxide in the mixed solution is 1: 1.
7. the composite material of silicon monoxide coated with nitrogen-doped carbon material as claimed in claim 1 or 4, wherein in S1, the weight ratio of graphite, concentrated sulfuric acid and mixed solution is 1: 2-6: 1 to 4.
8. The composite material of the nitrogen-doped carbon material coated with the silicon monoxide as claimed in claim 1 or 4, wherein in S1, concentrated sulfuric acid is added for ball milling for 3-10 h, then mixed liquid of benzoyl peroxide and hydrogen peroxide is added, and the ball milling is continued for 5-48 h to obtain graphene oxide slurry.
9. The nitrogen-doped carbon material-coated silica composite material as claimed in claim 1, wherein in S2, the weight ratio of pitch to oxidant is 1: 0.5 to 3.
10. The nitrogen-doped carbon material-coated silica composite material according to claim 1, wherein the pitch in S2 is one or a mixture of two or more of coal pitch, petroleum pitch, and natural pitch.
11. The nitrogen-doped carbon material-coated silica composite material as claimed in claim 1, wherein in S2, the oxidant is one or a mixture of more than two of hydrogen peroxide, benzoyl peroxide and concentrated sulfuric acid.
12. The composite material of claim 1, wherein the temperature of heating and stirring in S2 is 50-80 ℃ and the time of heating and stirring is 2-7 h.
13. The nitrogen-doped carbon material-coated silica composite material according to claim 1, wherein in S3, the weight ratio of silica to melamine is 1: 0.1 to 1.5.
14. The composite material of claim 1, wherein the drying temperature in S3 is 75-85 ℃ and the drying time is 10-14 h.
15. The composite material of claim 1, wherein the ammonia gas is introduced at a flow rate of 200mL/min for 10min in S4.
16. The composite material of claim 1, wherein the reaction time of the S4 is 1-10 h.
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| CN108807896B (en) * | 2018-06-11 | 2020-10-23 | 清华大学深圳研究生院 | Preparation method of nitrogen-doped carbon-coated silicon-carbon composite material |
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