CN113851635A - Silicon-carbon composite negative electrode material for lithium ion battery, preparation method of silicon-carbon composite negative electrode material and battery - Google Patents
Silicon-carbon composite negative electrode material for lithium ion battery, preparation method of silicon-carbon composite negative electrode material and battery Download PDFInfo
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- CN113851635A CN113851635A CN202010596706.4A CN202010596706A CN113851635A CN 113851635 A CN113851635 A CN 113851635A CN 202010596706 A CN202010596706 A CN 202010596706A CN 113851635 A CN113851635 A CN 113851635A
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- silicon
- carbon composite
- lithium ion
- negative electrode
- ion battery
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a silicon-carbon composite negative electrode material for a lithium ion battery, a preparation method thereof and the battery, wherein the preparation method of the silicon-carbon composite negative electrode material for the lithium ion battery is characterized in that a foaming agent, an organic polymer and asphalt are coated on the surface of a silicon by a solid-phase reaction method to prepare the silicon-carbon composite negative electrode material for the lithium ion battery; the silicon-carbon composite negative electrode material for the lithium ion battery is of a core-shell structure, the core-shell structure comprises a Si/C core and a carbon coating layer coated on the surface of the Si/C core, the Si/C core is a core with Si distributed on the surface of graphite, and a cavity is formed between the Si/C core and the carbon coating layer. The preparation method is simple and convenient in process, environment-friendly, pollution-free and easy to realize large-scale production, and the prepared silicon-carbon composite negative electrode material for the lithium ion battery has enough volume expansion cavities, so that the volume expansion of silicon can be relieved, the conductivity of the negative electrode material is effectively improved, and the electrochemical performance of the lithium ion battery is further improved.
Description
Technical Field
The invention relates to the field of battery material manufacturing, in particular to a silicon-carbon composite negative electrode material for a lithium ion battery and a preparation method thereof.
Background
With the rapid development and wide application of various portable electronic devices and new energy vehicles in recent decades, people have made higher requirements on the charge and discharge performance and capacity of lithium ion secondary batteries, but the currently used anode and cathode materials of lithium ion batteries are increasingly unable to meet the requirements. Improving the electrochemical performance of the lithium ion secondary battery is the most convenient and efficient means for improving the anode and cathode materials (particularly the cathode). At present, natural graphite, modified graphite, mesocarbon microbeads, soft carbon, hard carbon and the like are generally adopted in commercial lithium ion secondary batteries, however, the specific capacity of the materials is too low (such as the theoretical capacity of the graphite 372mAh/g) to meet the requirement of high-energy density batteries, and therefore, the development of a novel negative electrode with high specific capacity is attracted attention.
The silicon-based negative electrode material has the advantages of high lithium storage capacity (4200mAh/g), low lithium intercalation potential, abundant reserves in a ground shell and the like, but the silicon-based negative electrode material can cause pulverization of the silicon-based negative electrode material and falling of active substances from a current collector along with large volume change (more than 300%) in the charging and discharging processes, and the conductivity is poor, so that the electrode cycle performance is poor. In recent years, researchers have tried many new methods and technologies to modify the volume effect and conductivity of silicon-based materials, wherein the preparation of core-shell silicon-carbon composite materials is an effective method, and the synergistic effect among the components of the composite materials is utilized to improve the volume expansion problem of the materials in the charge and discharge processes and improve the conductivity of silicon cathodes.
In recent years, with the development of lithium battery technology, some methods for synthesizing carbon-coated silicon negative electrode materials have appeared, such asApplication No. 201510129121.0 discloses a silicon-carbon composite material and a preparation method thereof and application thereof in a lithium ion battery, application No. 201410025915.8 discloses a hollow structure material and a preparation method and application thereof, application No. 201610139926.8 discloses a preparation method of a silicon-based negative electrode material, a negative electrode material and a battery, application No. 201811543711.8 discloses a negative electrode material for a battery and a manufacturing method thereof, a negative electrode for a secondary battery and a secondary battery, application No. 201180059560.9 discloses a negative electrode material for a lithium ion secondary battery and a manufacturing method thereof, a negative electrode for a lithium ion secondary battery and a lithium ion secondary battery, application No. 201310449500.9 discloses a negative electrode active material for a lithium ion battery and a preparation method thereof, a negative electrode, a lithium ion battery and the like, and the following problems occur in the methods: (1) the carbon-coated silicon negative electrode material synthesized by the traditional method only contains a core-shell structure and cannot leave a volume expansion space for the material, so that the electrochemical performance is poor; (2) by means of SiO2Coating, and then synthesizing the carbon-coated silicon-carbon cathode material by a carbon coating method, wherein hydrofluoric acid etching is further adopted, so that the process is increased, and the environment is harmed; (3) naphthalene and methylnaphthalene are used as pore-forming agents, so that the process is complex, raw material waste is caused, and the method is usually suitable for synthesis in a laboratory and cannot realize commercial production.
In view of the above, it is desirable to develop a new negative electrode material and a preparation method thereof, which can alleviate the problem of poor lithium ion electrochemical performance caused by expansion of the silicon negative electrode material and improve the conductivity of the negative electrode material, thereby improving the electrochemical performance of the lithium ion battery, and on the other hand, the preparation method of the new negative electrode material is simple, environment-friendly and relatively low in cost.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a silicon-carbon composite negative electrode material for a lithium ion battery and a preparation method thereof, wherein the preparation method adopts a solid-phase reaction method to coat a foaming agent, an organic polymer and asphalt on the surface of silicon to prepare the silicon-carbon composite negative electrode material for the lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a silicon-carbon composite negative electrode material for a lithium ion battery, which is of a core-shell structure, wherein the core-shell structure comprises a Si/C core and a carbon coating layer coated on the surface of the Si/C core, the Si/C core is a core with Si distributed on the surface of graphite, and a cavity is formed between the Si/C core and the carbon coating layer.
Preferably, the silicon-carbon composite negative electrode material for the lithium ion battery comprises the following components in percentage by mass: 10-80% of graphite, 5-25% of silicon and 5-10% of pyrolytic carbon.
Preferably, the silicon is selected from one of monocrystalline silicon, polycrystalline silicon, and porous silicon; and/or
The graphite is selected from one of natural graphite and artificial graphite.
Preferably, the particle size of the silicon-carbon composite negative electrode material for the lithium ion battery is 5-16 μm.
The second aspect of the invention provides a battery, which comprises the silicon-carbon composite negative electrode material for the lithium ion battery.
The third aspect of the invention provides a preparation method of the silicon-carbon composite negative electrode material for the lithium ion battery, which is characterized in that a foaming agent, an organic polymer and asphalt are coated on the surface of a silicon by a solid-phase reaction method to prepare the silicon-carbon composite negative electrode material for the lithium ion battery.
Preferably, the method comprises the following steps:
s1, preparing a silicon/graphite/carbon composite material by adopting a solid-phase reaction method, and performing primary ball milling on silicon and graphite to obtain silicon/graphite composite particles; then adding organic polymer and foaming agent to perform secondary ball milling and foaming pore-forming, and performing primary heat treatment to obtain a silicon/graphite/carbon composite material;
and S2, performing third ball milling, kneading and stirring on the silicon/graphite/carbon composite material and asphalt, and performing second heat treatment to obtain the silicon-carbon composite negative electrode material for the lithium ion battery.
Preferably, in the step S1, the silicon is selected from one of monocrystalline silicon, polycrystalline silicon and porous silicon;
the graphite is selected from one of natural graphite and artificial graphite;
the organic polymer is selected from one of polyvinyl alcohol, polyvinylpyrrolidone, polystyrene, polyvinyl chloride, polyacrylonitrile, polytetrafluoroethylene, polyvinyl acetate, polyacrylic acid and ester thereof, polymethacrylic acid and ester thereof, carboxymethyl cellulose, phenolic resin, urea-formaldehyde resin, furfural resin, epoxy resin, polyacrylonitrile, polyacrylamide, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, ABS resin, glucose-like, sucrose, fructose, cellulose and starch;
the foaming agent is selected from one of ammonia borane, hydrazine borane, dimethylamine borane, triethylammonia borane, azodicarbonamide, azodiisobutyronitrile, diisopropyl azodicarboxylate, benzenesulfonic acid hydrazine, p-toluenesulfonic acid hydrazine, dinitrosopentamethylenetetramine, nitrosoterephthalamide, diazoaminobenzene, azodicarboxylate, 1, 3-benzenesulfonic acid hydrazine, trihydrazino-s-triazine, N-nitrourea, N-nitroguanidine, sulfonic acid semicarbazide, p-methylsulfonic acid azide, biphenyl-N, N-sulfonic acid azide and p-methylsulfonic acid acetone hydrazone.
Preferably, the silicon is nano elemental silicon.
Preferably, the particle size of the silicon is 20-200 nm; and/or
The particle size of the graphite is 1-15 mu m.
Preferably, the particle size of the silicon is 30-150 nm; and/or
The particle size of the graphite is 2-10 mu m.
Preferably, in the processes of the first ball milling, the second ball milling and the third ball milling, the ball-to-material ratio is 5-200, the ball milling time is 0.1-18 h, and the ball milling rotating speed is 100-1000 r/min.
Preferably, in the step S1, the temperature of the foaming and pore-forming is 100 to 300 ℃, and/or
In the step S2, the softening point of the asphalt is 100-300 ℃, the kneading and stirring temperature is 100-300 ℃, and the kneading and stirring speed is 50-500 rpm.
Preferably, in the first heat treatment and the second heat treatment, the temperature is 600-1000 ℃, the treatment time is 0.5-6 h, the heating rate is 1-10 ℃/min, and/or
And in the first heat treatment and the second heat treatment, the atmosphere is one or more of carbon dioxide, argon, nitrogen, helium, ammonia, hydrogen and vacuum.
The invention has the beneficial effects that:
1. according to the preparation method of the silicon-carbon composite negative electrode material for the lithium ion battery, the foaming agent, the organic polymer and the asphalt are coated on the surface of the silicon by adopting a solid-phase reaction, and after the silicon is carbonized by heat treatment, not only can enough volume expansion cavities be reserved for the silicon, the volume expansion of the silicon is effectively relieved, and an active substance is placed to fall off from a current collector, so that the smoothness of the whole electrode conductive network is kept, the silicon is prevented from being agglomerated in the circulation process, the silicon is prevented from directly contacting with electrolyte, and the circulation performance of the lithium ion battery is greatly improved;
2. the silicon-carbon composite negative electrode material for the lithium ion battery has high conductivity, and a large amount of N, S, B and other doping elements are introduced into a carbon coating layer of the silicon-carbon composite negative electrode material for the lithium ion battery, so that the conductivity of a carbon material can be improved, and the impedance and the polarization degree can be effectively reduced, so that the electrochemical performance of the lithium ion battery can be improved;
3. the preparation method of the silicon-carbon composite negative electrode material for the lithium ion battery is simple and convenient in process, environment-friendly and pollution-free, and easy to realize large-scale production.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
fig. 1 is an XRD spectrum of the silicon-carbon composite negative electrode material for lithium ion battery prepared in example 1;
fig. 2 is a graph showing electrochemical properties of the silicon-carbon composite anode material for a lithium ion battery prepared in example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way.
According to the preparation method of the silicon-carbon composite negative electrode material for the lithium ion battery, the silicon surface is coated with the foaming agent, the organic polymer and the asphalt through a solid-phase reaction method to prepare the silicon-carbon composite negative electrode material for the lithium ion battery; the silicon-carbon composite negative electrode material for the lithium ion battery is of a core-shell structure, the core-shell structure comprises a Si/C core and a carbon coating layer coated on the surface of the Si/C core, the Si/C core is a core with Si distributed on the surface of graphite, and a cavity is formed between the Si/C core and the carbon coating layer.
The preparation method comprises the following steps:
s1, preparing a silicon/graphite/carbon composite material by adopting a solid-phase reaction method, and performing primary ball milling on silicon and graphite to obtain silicon/graphite composite particles; then adding organic polymer and foaming agent to perform secondary ball milling and foaming pore-forming, and performing primary heat treatment to obtain a silicon/graphite/carbon composite material;
wherein the silicon is selected from one of monocrystalline silicon, polycrystalline silicon and porous silicon; further silicon adopts nano simple substance silicon; the particle size of the silicon is 20-200 nm, and further the particle size of the silicon is 30-150 nm;
the graphite is selected from one of natural graphite and artificial graphite, the particle size of the graphite is 1-15 mu m, and further the particle size of the graphite is 2-10 mu m;
the organic polymer is selected from one of polyvinyl alcohol, polyvinylpyrrolidone, polystyrene, polyvinyl chloride, polyacrylonitrile, polytetrafluoroethylene, polyvinyl acetate, polyacrylic acid and ester thereof, polymethacrylic acid and ester thereof, carboxymethyl cellulose, phenolic resin, urea-formaldehyde resin, furfural resin, epoxy resin, polyacrylonitrile, polyacrylamide, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, ABS resin, glucose-like, sucrose, fructose, cellulose and starch;
the foaming agent is selected from one of ammonia borane, hydrazine borane, dimethylamine borane, triethylammonia borane, azodicarbonamide, azodiisobutyronitrile, diisopropyl azodicarboxylate, benzenesulfonic acid hydrazine, p-toluenesulfonic acid hydrazine, dinitrosopentamethylenetetramine, nitrosoterephthalamide, diazoaminobenzene, azodicarboxylate, 1, 3-benzenesulfonic acid hydrazine, trihydrazino-s-triazine, N-nitrourea, N-nitroguanidine, sulfonic acid semicarbazide, p-methylsulfonic acid azide, biphenyl-N, N-sulfonic acid azide and p-methylsulfonic acid acetone hydrazone;
in the first ball milling process and the second ball milling process, the ball-material ratio is 5-200, the ball milling time is 0.1-18 h, and the ball milling rotating speed is 100-1000 r/min; the temperature of foaming and pore-forming is 100-300 ℃; in the first heat treatment process, the temperature is 600-1000 ℃, the treatment time is 0.5-6 h, the heating rate is 1-10 ℃/min, and the atmosphere is one or more of carbon dioxide, argon, nitrogen, helium, ammonia, hydrogen and vacuum.
And S2, performing third ball milling, kneading and stirring on the silicon/graphite/carbon composite material and the asphalt, and performing second heat treatment to obtain the silicon-carbon composite negative electrode material for the lithium ion battery.
In the third ball milling process, the ball-material ratio is 5-200, the ball milling time is 0.1-18 h, and the ball milling speed is 100-1000 r/min; the softening point of the asphalt is 100-300 ℃, the kneading and stirring temperature is 100-300 ℃, and the kneading and stirring speed is 50-500 revolutions per minute;
in the second heat treatment process, the temperature is 600-1000 ℃, the treatment time is 0.5-6 h, the heating rate is 1-10 ℃/min, and the atmosphere is one or more of carbon dioxide, argon, nitrogen, helium, ammonia, hydrogen and vacuum.
The silicon-carbon composite negative electrode material for the lithium ion battery prepared by the steps comprises the following components in percentage by mass: 10-80% of graphite, 5-25% of silicon and 5-10% of pyrolytic carbon; the silicon-carbon composite negative electrode material for the lithium ion battery has the granularity of 5-16 mu m and the specific surfaceProduct of 2m2g, the first effect is more than 76 percent; the silicon-carbon composite negative electrode material for the lithium ion battery can be used for preparing the battery.
Example 1
Adding 1g of nano silicon powder (the particle size of the nano silicon powder is 30-150 nm) and 8g of natural graphite (the particle size is 2 microns) into a ball mill, adding zirconia balls according to the ball-to-material ratio of 50:1, carrying out first ball milling by the ball mill at the rotating speed of 500 rpm for 1 hour to obtain silicon/graphite composite particles; then adding 0.2g of azodicarbonamide and 1g of styrene butadiene rubber into the ball mill for secondary ball milling, sending mixed powder subjected to secondary ball milling into a tube furnace after 6 hours, and preserving heat for 2 hours at 200 ℃ in a vacuum atmosphere for foaming and pore-forming to fully decompose azodicarbonamide for foaming; then, under the argon atmosphere, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain a powdery silicon/graphite/carbon composite material;
feeding the powdery silicon/graphite/carbon composite material and 0.3g of asphalt into a ball mill, adding zirconia balls according to a ball-to-material ratio of 40:1, carrying out third ball milling by the ball mill at a rotating speed of 300 revolutions per minute, feeding mixed powder subjected to third ball milling into a kneading kettle after 12 hours, kneading and stirring for 2 hours at 300 ℃, then feeding the mixed powder subjected to kneading and stirring into a tubular furnace for second heat treatment, and carrying out carbonization for 2 hours at a temperature rising rate of 5 ℃/min to 900 ℃ under an argon atmosphere to obtain the silicon-carbon composite negative electrode material for the lithium ion battery;
the silicon-carbon composite negative electrode material for the lithium ion battery prepared by the embodiment has a core-shell structure and comprises a Si/C core and a carbon coating layer, wherein the carbon coating layer can completely coat the Si/C core, and a partial cavity is formed between the Si/C core and the carbon coating layer; the physical and electrochemical characteristics of the silicon-carbon composite negative electrode material for the lithium ion battery are shown in table 1.
Example 2
Adding 1g of nano silicon powder (the particle size of the nano silicon powder is 30-150 nm) and 8g of artificial graphite (the particle size is 3 microns) into a ball mill, adding zirconia balls according to the ball-to-material ratio of 30:1, carrying out primary ball milling by the ball mill at the rotating speed of 350 revolutions per minute for 2 hours to obtain silicon/graphite composite particles; then adding 0.3g of ammonia borane and 0.5g of polyvinylpyrrolidone into the ball mill for secondary ball milling, sending the mixed powder subjected to secondary ball milling into a tube furnace after 5h, and preserving heat for 2h at 150 ℃ in a vacuum atmosphere for foaming and pore-forming to fully decompose and foam the ammonia borane; then heating to 750 ℃ at a heating rate of 10 ℃/min under an argon atmosphere, preserving the heat for 2h, and cooling to room temperature to obtain a powdery silicon/graphite/carbon composite material;
feeding the powdery silicon/graphite/carbon composite material and 0.25g of asphalt into a ball mill, adding zirconia balls according to a ball-to-material ratio of 40:1, carrying out third ball milling by the ball mill at a rotating speed of 350 revolutions per minute, feeding mixed powder subjected to third ball milling into a kneading kettle after 12 hours, kneading and stirring for 2 hours at 300 ℃, then feeding the mixed powder subjected to kneading and stirring into a tubular furnace for second heat treatment, and carrying out carbonization for 2 hours at a heating rate of 5 ℃/min to 950 ℃ under a nitrogen atmosphere to obtain the silicon-carbon composite negative electrode material for the lithium ion battery;
the silicon-carbon composite negative electrode material for the lithium ion battery prepared by the embodiment has a core-shell structure and comprises a Si/C core and a carbon coating layer, wherein the carbon coating layer can completely coat the Si/C core, and a partial cavity is formed between the Si/C core and the carbon coating layer; the physical and electrochemical characteristics of the silicon-carbon composite negative electrode material for the lithium ion battery are shown in table 1.
Example 3
Adding 1g of nano silicon powder (the particle size of the nano silicon powder is 30-150 nm) and 7.5g of artificial graphite (the particle size is 5 microns) into a ball mill, adding zirconia balls according to the ball-to-material ratio of 40:1, carrying out first ball milling by the ball mill at the rotating speed of 400 rpm for 2 hours to obtain silicon/graphite composite particles; then adding 0.25g of azobisisobutyronitrile and 0.5g of epoxy resin into the ball mill for secondary ball milling, sending the mixed powder subjected to secondary ball milling into a tube furnace after 6 hours, and preserving heat for 2 hours at 120 ℃ in a vacuum atmosphere for foaming and pore-forming to fully decompose and foam the azobisisobutyronitrile; then, under the argon atmosphere, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain a powdery silicon/graphite/carbon composite material;
feeding the powdery silicon/graphite/carbon composite material and 0.2g of asphalt into a ball mill, adding zirconia balls according to a ball-to-material ratio of 40:1, carrying out third ball milling by the ball mill at a rotating speed of 400 rpm, feeding mixed powder subjected to third ball milling into a kneading kettle after 12 hours, kneading and stirring for 2 hours at 300 ℃, then feeding the kneaded and stirred mixed powder into a tubular furnace for second heat treatment, and carrying out carbonization for 2 hours at a heating rate of 5 ℃/min to 900 ℃ under an argon atmosphere to obtain the silicon-carbon composite negative electrode material for the lithium ion battery;
the silicon-carbon composite negative electrode material for the lithium ion battery prepared by the embodiment has a core-shell structure and comprises a Si/C core and a carbon coating layer, wherein the carbon coating layer can completely coat the Si/C core, and a partial cavity is formed between the Si/C core and the carbon coating layer; the physical and electrochemical characteristics of the silicon-carbon composite negative electrode material for the lithium ion battery are shown in table 1.
Example 4
Adding 1g of nano silicon powder (the particle size of the nano silicon powder is 30-150 nm) and 8.5g of natural graphite (the particle size is 6 microns) into a ball mill, adding zirconia balls according to the ball-to-material ratio of 40:1, carrying out first ball milling by the ball mill at the rotating speed of 350 revolutions per minute for 2 hours to obtain silicon/graphite composite particles; then adding 0.15g of diisopropyl azodicarboxylate and 0.5g of polyacrylonitrile into the ball mill for secondary ball milling, sending the mixed powder subjected to secondary ball milling into a tube furnace after 6 hours, and preserving heat for 2 hours at 240 ℃ in a vacuum atmosphere for foaming and pore-forming to fully decompose and foam the diisopropyl azodicarboxylate; then, under the atmosphere of ammonia gas, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain a powdery silicon/graphite/carbon composite material;
feeding the powdery silicon/graphite/carbon composite material and 0.4g of asphalt into a ball mill, adding zirconia balls according to a ball-to-material ratio of 40:1, carrying out third ball milling by the ball mill at a rotating speed of 350 revolutions per minute, feeding mixed powder subjected to third ball milling into a kneading kettle after 18 hours, kneading and stirring for 2 hours at 250 ℃, then feeding the mixed powder subjected to kneading and stirring into a tubular furnace for second heat treatment, and carrying out high-temperature carbonization for 3 hours at a heating rate of 2 ℃/min to 800 ℃ under a helium atmosphere to obtain the silicon-carbon composite negative electrode material for the lithium ion battery;
the silicon-carbon composite negative electrode material for the lithium ion battery prepared by the embodiment has a core-shell structure and comprises a Si/C core and a carbon coating layer, wherein the carbon coating layer can completely coat the Si/C core, and a cavity enough for silicon volume expansion is formed between the Si/C core and the carbon coating layer; the physical and electrochemical characteristics of the silicon-carbon composite negative electrode material for the lithium ion battery are shown in table 1.
Example 5
Adding 1g of nano silicon powder (the particle size of the nano silicon powder is 30-150 nm) and 9g of artificial graphite (the particle size is 10 microns) into a ball mill, adding zirconia balls according to the ball-to-material ratio of 30:1, carrying out primary ball milling by the ball mill at the rotating speed of 250 revolutions per minute for 2 hours to obtain silicon/graphite composite particles; then adding 0.5g of hydrazine benzenesulfonate and 0.5g of polyvinyl alcohol into the ball mill for secondary ball milling, sending the mixed powder subjected to secondary ball milling into a tube furnace after 4 hours, and preserving heat for 4 hours at 100 ℃ in a vacuum atmosphere for foaming and pore-forming to fully decompose and foam the hydrazine benzenesulfonate; then, under the atmosphere of carbon dioxide, heating to 750 ℃ at the heating rate of 2 ℃/min, preserving the heat for 2h, and cooling to room temperature to obtain a powdery silicon/graphite/carbon composite material;
feeding the powdery silicon/graphite/carbon composite material and 0.5g of asphalt into a ball mill, adding zirconia balls according to a ball-to-material ratio of 40:1, carrying out third ball milling by the ball mill at a rotating speed of 250 revolutions per minute, feeding mixed powder subjected to third ball milling into a kneading kettle after 12 hours, kneading and stirring for 2 hours at 300 ℃, then feeding the kneaded and stirred mixed powder into a tubular furnace for second heat treatment, and carrying out carbonization for 2 hours at a heating rate of 5 ℃/min to 950 ℃ under an argon atmosphere to obtain the silicon-carbon composite negative electrode material for the lithium ion battery;
the silicon-carbon composite negative electrode material for the lithium ion battery prepared by the embodiment has a core-shell structure and comprises a Si/C core and a carbon coating layer, wherein the carbon coating layer can completely coat the Si/C core, and a partial cavity is formed between the Si/C core and the carbon coating layer; the physical and electrochemical characteristics of the silicon-carbon composite negative electrode material for the lithium ion battery are shown in table 1.
Example 6
Adding 1g of nano silicon powder (the particle size of the nano silicon powder is 30-150 nm) and 7.5g of natural graphite (the particle size is 2 microns) into a ball mill, adding zirconia balls according to the ball-to-material ratio of 40:1, carrying out first ball milling by the ball mill at the rotating speed of 300 revolutions per minute for 2 hours to obtain silicon/graphite composite particles; then adding 0.4g of dinitrosopentamethylenetetramine and 0.5g of cellulose into the ball mill for secondary ball milling, sending mixed powder subjected to secondary ball milling into a tube furnace after 6 hours, and preserving heat for 2 hours at 200 ℃ in a vacuum atmosphere for foaming and pore-forming to fully decompose and foam the dinitrosopentamethylenetetramine; then heating to 800 ℃ at a heating rate of 3 ℃/min under an argon atmosphere, preserving heat for 3h, and cooling to room temperature to obtain a powdery silicon/graphite/carbon composite material;
feeding the powdery silicon/graphite/carbon composite material and 0.6g of asphalt into a ball mill, adding zirconia balls according to a ball-to-material ratio of 40:1, carrying out third ball milling by the ball mill at a rotating speed of 300 revolutions per minute, feeding mixed powder subjected to third ball milling into a kneading kettle after 12 hours, kneading and stirring for 2 hours at 300 ℃, then feeding the mixed powder subjected to kneading and stirring into a tubular furnace for second heat treatment, and carrying out high-temperature carbonization for 3 hours at a heating rate of 2 ℃/min to 800 ℃ under a helium atmosphere to obtain the silicon-carbon composite negative electrode material for the lithium ion battery;
the silicon-carbon composite negative electrode material for the lithium ion battery prepared by the embodiment has a core-shell structure and comprises a Si/C core and a carbon coating layer, wherein the carbon coating layer can completely coat the Si/C core, and a partial cavity is formed between the Si/C core and the carbon coating layer; the physical and electrochemical characteristics of the silicon-carbon composite negative electrode material for the lithium ion battery are shown in table 1.
TABLE 1
| Examples | Specific surface area (m)2/g) | Particle size (. mu.m) | 0.2C capacity (mAh/g) | First effect (%) |
| Example 1 | 1.9 | 5.6 | 1634 | 76 |
| Example 2 | 1.5 | 7.2 | 1689 | 77 |
| Example 3 | 1.3 | 8.7 | 1748 | 77 |
| Example 4 | 1.1 | 9.4 | 1604 | 78 |
| Example 5 | 0.98 | 12.6 | 1596 | 79 |
| Example 6 | 1.6 | 5.7 | 1656 | 76 |
As shown in fig. 1, the XRD diffraction peak shown in the XRD spectrum of the silicon-carbon composite negative electrode material for lithium ion battery prepared in example 1 is the diffraction peak of silicon and graphite; as shown in FIG. 2, the negative electrode made of the Si-C composite negative electrode material for lithium ion battery prepared in example 1 was coated with 0.2Ag-1Charging and discharging at current density, and after 100 times of circulation, the capacity is still maintained at 1608mAhg-1The coulombic efficiency remained at 100%. With reference to table 1, the silicon-carbon composite negative electrode materials for lithium ion batteries prepared in examples 1 to 6 have a specific surface area of 2m2Less than g, particle size of 5-16 μm, first effect of more than 76%, and discharge capacity of 1590-1750 mAhg at 0.2C rate-1In the meantime.
With the comprehensive embodiments of 1-6, the preparation method of the silicon-carbon composite negative electrode material for the lithium ion battery, disclosed by the invention, has the advantages that the foaming agent, the organic polymer and the asphalt are coated on the surface of the silicon by adopting a solid-phase reaction method, and after the silicon is carbonized by heat treatment, not only can enough volume expansion cavities be reserved for the silicon, but also the volume expansion of the silicon is effectively relieved, the active substances are placed to fall off from a current collector, so that the smoothness of a whole electrode conductive network is kept conveniently, the silicon can be prevented from being agglomerated in the circulating process, the silicon is prevented from being in direct contact with an electrolyte, and the circulating performance of the lithium ion battery is greatly improved; the silicon-carbon composite negative electrode material for the lithium ion battery has high conductivity, and a large amount of N, S, B and other doping elements are introduced into a carbon coating layer of the silicon-carbon composite negative electrode material for the lithium ion battery, so that the conductivity of a carbon material can be improved, and the impedance and the polarization degree are effectively reduced, so that the electrochemical performance of the lithium ion battery is improved; the preparation method of the silicon-carbon composite negative electrode material for the lithium ion battery is simple and convenient in process, environment-friendly and pollution-free, and easy to realize large-scale production.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (14)
1. The silicon-carbon composite negative electrode material for the lithium ion battery is characterized by being of a core-shell structure, wherein the core-shell structure comprises a Si/C core and a carbon coating layer coated on the surface of the Si/C core, the Si/C core is a core with Si distributed on the surface of graphite, and a cavity is formed between the Si/C core and the carbon coating layer.
2. The silicon-carbon composite anode material for the lithium ion battery according to claim 1, wherein the silicon-carbon composite anode material for the lithium ion battery comprises the following components in percentage by mass: 10-80% of graphite, 5-25% of silicon and 5-10% of pyrolytic carbon.
3. The silicon-carbon composite anode material for the lithium ion battery according to claim 2, wherein the silicon is selected from one of single crystal silicon, polycrystalline silicon and porous silicon; and/or
The graphite is selected from one of natural graphite and artificial graphite.
4. The silicon-carbon composite negative electrode material for the lithium ion battery according to claim 1, wherein the particle size of the silicon-carbon composite negative electrode material for the lithium ion battery is 5 to 16 μm.
5. A battery comprising the silicon-carbon composite negative electrode material for a lithium ion battery according to any one of claims 1 to 4.
6. The preparation method of the silicon-carbon composite negative electrode material for the lithium ion battery as claimed in any one of claims 1 to 4, characterized in that the silicon surface is coated with a foaming agent, an organic polymer and asphalt by a solid phase reaction method to prepare the silicon-carbon composite negative electrode material for the lithium ion battery.
7. The method of claim 6, comprising the steps of:
s1, preparing a silicon/graphite/carbon composite material by adopting a solid-phase reaction method, and performing primary ball milling on silicon and graphite to obtain silicon/graphite composite particles; then adding organic polymer and foaming agent to perform secondary ball milling and foaming pore-forming, and performing primary heat treatment to obtain a silicon/graphite/carbon composite material;
and S2, performing third ball milling, kneading and stirring on the silicon/graphite/carbon composite material and asphalt, and performing second heat treatment to obtain the silicon-carbon composite negative electrode material for the lithium ion battery.
8. The method according to claim 7, wherein in step S1, the silicon is selected from one of single crystal silicon, polycrystalline silicon, and porous silicon;
the graphite is selected from one of natural graphite and artificial graphite;
the organic polymer is selected from one of polyvinyl alcohol, polyvinylpyrrolidone, polystyrene, polyvinyl chloride, polyacrylonitrile, polytetrafluoroethylene, polyvinyl acetate, polyacrylic acid and ester thereof, polymethacrylic acid and ester thereof, carboxymethyl cellulose, phenolic resin, urea-formaldehyde resin, furfural resin, epoxy resin, polyacrylonitrile, polyacrylamide, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, ABS resin, glucose-like, sucrose, fructose, cellulose and starch;
the foaming agent is selected from one of ammonia borane, hydrazine borane, dimethylamine borane, triethylammonia borane, azodicarbonamide, azodiisobutyronitrile, diisopropyl azodicarboxylate, benzenesulfonic acid hydrazine, p-toluenesulfonic acid hydrazine, dinitrosopentamethylenetetramine, nitrosoterephthalamide, diazoaminobenzene, azodicarboxylate, 1, 3-benzenesulfonic acid hydrazine, trihydrazino-s-triazine, N-nitrourea, N-nitroguanidine, sulfonic acid semicarbazide, p-methylsulfonic acid azide, biphenyl-N, N-sulfonic acid azide and p-methylsulfonic acid acetone hydrazone.
9. The method of claim 8, wherein the silicon is nano elemental silicon.
10. The method according to claim 8, wherein the silicon has a particle size of 20 to 200 nm; and/or
The particle size of the graphite is 1-15 mu m.
11. The method according to claim 10, wherein the silicon has a particle size of 30 to 150 nm; and/or
The particle size of the graphite is 2-10 mu m.
12. The preparation method of claim 7, wherein in the first ball milling process, the second ball milling process and the third ball milling process, the ball-to-material ratio is 5-200, the ball milling time is 0.1-18 h, and the ball milling speed is 100-1000 rpm.
13. The preparation method according to claim 7, wherein in the step S1, the temperature of the foaming pore-forming is 100-300 ℃, and/or
In the step S2, the softening point of the asphalt is 100-300 ℃, the kneading and stirring temperature is 100-300 ℃, and the kneading and stirring speed is 50-500 rpm.
14. The method according to claim 7, wherein the first heat treatment and the second heat treatment are carried out at 600 to 1000 ℃, the treatment time is 0.5 to 6 hours, the temperature increase rate is 1 to 10 ℃/min, and/or
And in the first heat treatment and the second heat treatment, the atmosphere is one or more of carbon dioxide, argon, nitrogen, helium, ammonia, hydrogen and vacuum.
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| CN103346293A (en) * | 2013-06-28 | 2013-10-09 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery |
| CN107799728A (en) * | 2016-08-29 | 2018-03-13 | 南京安普瑞斯有限公司 | A kind of hollow Si-C composite material for lithium ion battery and preparation method thereof |
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| CN110844910A (en) * | 2019-11-19 | 2020-02-28 | 北京卫蓝新能源科技有限公司 | Preparation method of silicon-based negative electrode material of lithium ion battery |
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| CN103346293A (en) * | 2013-06-28 | 2013-10-09 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery |
| CN107799728A (en) * | 2016-08-29 | 2018-03-13 | 南京安普瑞斯有限公司 | A kind of hollow Si-C composite material for lithium ion battery and preparation method thereof |
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