CN113851634A - Core-shell structure silicon-carbon composite material for lithium ion battery, preparation method thereof and negative electrode - Google Patents

Core-shell structure silicon-carbon composite material for lithium ion battery, preparation method thereof and negative electrode Download PDF

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CN113851634A
CN113851634A CN202010596672.9A CN202010596672A CN113851634A CN 113851634 A CN113851634 A CN 113851634A CN 202010596672 A CN202010596672 A CN 202010596672A CN 113851634 A CN113851634 A CN 113851634A
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silicon
core
composite material
shell structure
carbon
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CN113851634B (en
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谭迎宾
李铮铮
吴若飞
陶军
杨兵
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Baowu Carbon Technology Co ltd
Baoshan Iron and Steel Co Ltd
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Abstract

Hair brushThe preparation method adopts phenol, aldehyde and polymer monomer to coat SiOxThen, preparing the core-shell structure silicon-carbon composite material for the lithium ion battery after acid treatment and heat treatment; the silicon-carbon composite material with the core-shell structure for the lithium ion battery is of a core-shell structure and comprises a silicon-based inner core, a first carbon coating layer and a second carbon coating layer, wherein the first carbon coating layer is coated on the surface of the silicon-based inner core, and the second carbon coating layer is coated outside the first carbon coating layer; the surface of the second carbon coating layer is provided with mesopores, and a cavity is arranged between the second carbon coating layer and the second carbon coating layer. The preparation method is simple and convenient in process, relatively low in cost and easy to realize large-scale production, the prepared silicon-carbon composite material with the core-shell structure for the lithium ion battery has enough space to relieve volume expansion in the charging and discharging process, and the silicon-carbon composite material with the core-shell structure for the lithium ion battery is applied to a lithium battery cathode and can show high first effect and charging and discharging capacity.

Description

Core-shell structure silicon-carbon composite material for lithium ion battery, preparation method thereof and negative electrode
Technical Field
The invention relates to the field of battery material manufacturing, in particular to a core-shell structure silicon-carbon composite material for a lithium ion battery, a preparation method thereof and a negative electrode.
Background
With the rapid development and wide application of various portable electronic devices and new energy automobiles in recent decades, people have made higher requirements on the charge and discharge performance and capacity of lithium ion secondary batteries, but the anode and cathode materials of the currently used lithium ion batteries can not meet the requirements more and more; the method is the most convenient and efficient means for improving the anode and cathode materials (particularly the cathode) by improving the electrochemical performance of the lithium ion secondary battery; at present, various carbon materials are generally adopted by commercial lithium ion secondary batteries as negative electrodes, such as natural graphite, modified graphite, mesocarbon microbeads, soft carbon, hard carbon and the like, but the specific capacity of the materials is too low (such as the theoretical capacity of the graphite 372mAh/g) to meet the requirement of a high-energy density battery, so that the development of a novel negative electrode for replacing the carbon materials 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 is poor in conductivity, and simultaneously, under the condition of lithium intercalation and deintercalation, along with large volume change (more than 300%), the silicon-based negative electrode material is pulverized and active substances fall off from a current collector, so that the electrode cycle performance is poor; in recent years, aiming at poor conductivity and serious volume effect of silicon materials, researchers try many new methods and technologies to modify the silicon materials so as to improve the cycle performance, wherein the preparation of the core-shell silicon-carbon composite material is an effective method, and the problem of volume expansion in the charge and discharge processes of the material is solved and the conductivity of a silicon cathode is improved by utilizing the synergistic effect among the components of the composite material.
In recent years, with the development of lithium battery technology, some methods for synthesizing carbon-coated silicon negative electrode materials have appeared, for example, application No. 201510129121.0 discloses a silicon-carbon composite material, a preparation method and application thereof in a lithium ion battery, application No. 201410025915.8 discloses a hollow structure material, 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, a secondary battery and the like, and the methods firstly adopt SiO2Coating a silicon material, then coating an organic carbon source, and finally synthesizing a carbon-coated negative electrode material by controlling the temperature and the atmosphere and etching with hydrofluoric acid, wherein the following problems can occur after the carbon-coated lithium battery negative electrode material is synthesized by adopting the method: (1) the conventional carbon coating only obtains a core-shell structure, and a volume expansion space cannot be reserved 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) the silicon material is oxidized on the surface of the silicon by adopting an oxidation method and then coated with the carbon material, so that the waste of the silicon material is seriously caused, the thickness of an oxide layer is not easy to control, the process is complex, and the method is usually suitable for synthesis in a laboratory and can not realize commercial production.
In view of the above circumstances, it is urgently needed to develop a novel silicon-carbon composite material and a preparation method thereof, which can alleviate the problem of poor lithium ion electrochemical performance caused by expansion in the charging and discharging processes of the silicon-carbon composite material and improve the conductivity of the silicon-carbon composite material, thereby improving the electrochemical performance of the lithium ion battery, and on the other hand, the preparation method is simple, the cost is relatively low, and the large-scale production is easy to realize.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a silicon-carbon composite material with a core-shell structure for a lithium ion battery, a preparation method thereof and a negative electrode, wherein the preparation method adopts phenolic resin and organic polymer to coat SiOxAnd then, the core-shell structure silicon-carbon composite material for the lithium ion battery is prepared by adopting acid treatment and heat treatment, the preparation method is simple and convenient in process, relatively low in cost and easy to realize large-scale production, the prepared core-shell structure silicon-carbon composite material for the lithium ion battery has enough space to relieve volume expansion in the charging and discharging process, and the core-shell structure silicon-carbon composite material for the lithium ion battery is applied to a lithium battery cathode and can show high first effect and charging and discharging capacity.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a core-shell structure silicon-carbon composite material for a lithium ion battery, which is of a core-shell structure and comprises a silicon-based core, a first carbon coating layer and a second carbon coating layer, wherein the first carbon coating layer is coated on the surface of the silicon-based core, and the second carbon coating layer is coated outside the first carbon coating layer; the surface of the second carbon cladding layer is provided with mesopores, and a cavity is arranged between the second carbon cladding layer and the second carbon cladding layer.
Preferably, the silicon-based inner core is SiOxX ranges from 0, 1, 2; the SiOxOne or more selected from elemental silicon, silicon monoxide and silicon dioxide.
The invention provides a negative electrode which comprises the core-shell structure silicon-carbon composite material for the lithium ion battery.
The third aspect of the invention provides a preparation method of a core-shell structure silicon-carbon composite material for a lithium ion battery, which adopts phenol, aldehyde and polymer monomer to coat SiOxThen the product is prepared by acid treatment and heat treatmentThe core-shell structure silicon-carbon composite material for the lithium ion battery.
Preferably, the method comprises the following steps:
s1, mixing SiOxUniformly dispersing the aqueous solution, adding phenol and aldehyde, and stirring to obtain the phenolic resin coated silicon-based composite material;
s2, adding a polymer monomer and an oxidant into the phenolic resin coated silicon-based composite material, and carrying out polymerization reaction to obtain a polymer/phenolic resin coated silicon-based composite material with mesopores;
s3, adding acid into the polymer/phenolic resin coated silicon-based composite material for acid treatment, removing the phenolic resin in the mesopores, and filtering and drying to obtain a silicon-carbon composite material intermediate with a core-shell structure;
and S4, performing heat treatment on the core-shell structure silicon-carbon composite material intermediate to obtain the core-shell structure silicon-carbon composite material for the lithium ion battery.
Preferably, in the step S1, the SiO is appliedxThe particle size of (A) is 1 nm-50 μm.
Preferably, in the step S1, the phenol is selected from one of phenol, cresol, xylenol, resorcinol, phloroglucinol, hydroquinone, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2, 3-diaminophenol, 2, 4-diaminophenol, 4-nitro-2-aminophenol, 5-nitro-2-aminophenol, 6-nitro-2-aminophenol, 4, 6-dinitro-2-aminophenol, 2-nitro-4-aminophenol, 5-nitro-2-aminophenol, 3-nitro-4-aminophenol, 4-sulfonamide-2-aminophenol, and/or
In the step S1, the aldehyde is selected from one of formaldehyde, paraformaldehyde, trioxymethylene, acetaldehyde and furfural, and/or
In the step S2, the polymer monomer is selected from one or more of pyrrole, aniline, thiophene, 3-methoxythiophene, 3, 4-ethylenedioxythiophene, and dopamine, and/or
In step S3, the acid is selected from one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, formic acid, and citric acid.
Preferably, in the step S2, the temperature of the polymerization reaction is 0 to 80 ℃, the reaction time is 0.1 to 12 hours, and the condition of the polymerization reaction is stirring or ultrasound.
Preferably, the stirring speed is 100-2000 rpm.
Preferably, in the step S4, in the heat treatment process, the temperature is 600 to 1000 ℃, the temperature rise rate is 1 to 10 ℃/min, the reaction time is 0.5 to 6 hours, and the atmosphere is selected from one or more of carbon dioxide, argon, nitrogen, helium, ammonia, hydrogen and vacuum.
The invention has the beneficial effects that:
1. the invention improves the existing method of the silicon-carbon cathode material with the core-shell structure, and the prepared silicon-carbon composite material with the core-shell structure for the lithium ion battery effectively improves the electrochemical performance of the lithium ion battery;
2. the invention relates to a preparation method of a silicon-carbon composite material with a core-shell structure for a lithium ion battery, which is characterized in that phenolic aldehyde and polymer monomers are polymerized to coat SiOxThe silicon-carbon composite material with the core-shell structure for the lithium ion battery is obtained through acid treatment and heat treatment, and the carbon coating layer of the silicon-carbon composite material with the core-shell structure for the lithium ion battery has a mesoporous aperture (the aperture is 2-50 nm), so that a rich and rapid channel is provided for acid treatment, a part of phenolic resin is conveniently removed, a cavity is reserved, and the problem of volume expansion of a silicon-based material is effectively solved;
3. the core-shell structure silicon-carbon composite material for the lithium ion battery has high conductivity, and a large amount of doping elements such as N, S and the like are introduced into the carbon coating layer of the core-shell structure silicon-carbon composite material for the lithium ion battery, so that the conductivity of the 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 is improved, a stable SEI film (solid electrolyte interface film) can be formed, the coulombic efficiency is improved, and the cycle performance of an electrode material is improved;
4. the preparation method of the core-shell structure silicon-carbon composite material for the lithium ion battery is simple and convenient in process, can be freely compounded with graphite, and is 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 a schematic structural diagram of a core-shell structure silicon-carbon composite material for lithium ion batteries prepared in embodiments 1 to 6;
fig. 2 is an XRD spectrum of the core-shell structure silicon-carbon composite material for the lithium ion battery prepared in example 1;
fig. 3 is an electrochemical performance diagram of the core-shell structure silicon-carbon composite material for the lithium ion battery prepared in example 2.
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.
As shown in fig. 1, the core-shell structure silicon-carbon composite material for a lithium ion battery provided by the invention is a core-shell structure, and comprises a silicon-based core 1, a first carbon coating layer 2 coated on the surface of the silicon-based core 1, and a second carbon coating layer 3 coated outside the first carbon coating layer 2; the surface of the second carbon coating layer 3 is provided with mesopores, and a cavity 4 is arranged between the first carbon coating layer 2 and the second carbon coating layer 3; the silicon-based core 1 is SiOxX is in the range of 0 to 2, SiOxOne or more selected from simple substance silicon, silicon monoxide and silicon dioxide; the core-shell structure silicon-carbon composite material for the lithium ion battery is applied to a lithium battery cathode, and can show high first-effect and charge-discharge capacity.
The invention provides a preparation method of a core-shell structure silicon-carbon composite material for a lithium ion battery, which adopts phenol, aldehyde and polymer monomer to coat SiOxThen, preparing the core-shell structure silicon-carbon composite material for the lithium ion battery through acid treatment and heat treatment; the preparation method comprises the following steps:
s1, mixing SiOxUniformly dispersing the aqueous solution, adding phenol and aldehyde, and stirring to obtain the phenolic resin coated silicon-based composite material; adding an alkaline catalyst in the process of forming phenolic resin by phenol and aldehyde, so that the thermosetting phenolic resin is coated on the surface of the silicon-based composite material conveniently; basic catalysisAgents such as ammonia, sodium hydroxide, etc.;
wherein SiO isxWherein x is in the range of 0 to 2, SiOxOne or more selected from elemental silicon, silicon monoxide and silicon dioxide. SiO 2xThe particle size of the particles is 1 nm-50 mu m;
the phenol is selected from one of phenol, cresol, xylenol, resorcinol, phloroglucinol, hydroquinone, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2, 3-diaminophenol, 2, 4-diaminophenol, 4-nitro-2-aminophenol, 5-nitro-2-aminophenol, 6-nitro-2-aminophenol, 4, 6-dinitro-2-aminophenol, 2-nitro-4-aminophenol, 5-nitro-2-aminophenol, 3-nitro-4-aminophenol and 4-sulfonamide-2-aminophenol;
the aldehyde is selected from one of formaldehyde, paraformaldehyde, trioxymethylene, acetaldehyde and furfural;
s2, adding a polymer monomer and an oxidant into the phenolic resin coated silicon-based composite material, and carrying out polymerization reaction to obtain a polymer/phenolic resin coated silicon-based composite material with mesopores;
wherein, the polymer monomer is selected from one or more of pyrrole, aniline, thiophene, 3-methoxythiophene, 3, 4-ethylenedioxythiophene and dopamine.
Carrying out polymerization reaction on the polymer monomer by stirring or ultrasound, wherein the temperature is 0-80 ℃ and the reaction time is 0.1-12 h in the process; when stirring is adopted, the stirring speed is 100-2000 rpm.
S3, adding acid into the polymer/phenolic resin coated silicon-based composite material for acid treatment, removing part of phenolic resin in the mesopores to form cavities, and filtering and drying to obtain a silicon-carbon composite material intermediate with a core-shell structure;
wherein the acid is selected from one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, formic acid and citric acid.
S4, performing heat treatment on the core-shell structure silicon-carbon composite material intermediate to obtain a core-shell structure silicon-carbon composite material for the lithium ion battery;
wherein in the heat treatment process, the temperature is 600-1000 ℃, the heating rate is 1-10 ℃/min, the reaction time is 0.5-6 h, and the atmosphere is selected from one or more of carbon dioxide, argon, nitrogen, helium, ammonia, hydrogen and vacuum.
Example 1
Adding 1gSi nano particles (50-150 nm) into 500mL of water, stirring for 3h to uniformly disperse the nano particles in an aqueous solution, adding 300mg of resorcinol and 0.3mL of formaldehyde solution into the solution, dropwise adding 0.2mL of ammonia water solution, and stirring for reacting for 60min to obtain the phenolic resin coated silicon-based composite material; adding 300 mu L of pyrrole and 0.2g of ammonium persulfate oxidant into the phenolic resin coated silicon-based composite material, stirring at the speed of 500 r/min at the temperature of 30 ℃, and stirring for 3 hours to obtain the polypyrrole/phenolic resin coated silicon-based composite material; adding 1mL of hydrochloric acid solution, stirring for 30min to remove part of phenolic resin, filtering and drying to obtain a silicon-carbon composite material intermediate with a core-shell structure; and (3) putting the core-shell structure silicon-carbon composite material intermediate into a tubular furnace for heat treatment, heating to 900 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, preserving the heat for 2h, and cooling to room temperature to obtain the core-shell structure silicon-carbon composite material for the lithium ion battery.
Example 2
Adding 1g of SiO particles (2 microns) into 500mL of water, stirring for 3h to uniformly disperse the particles in the water solution, adding 200mg of 3-aminophenol and 0.2mL of formaldehyde solution into the solution, dropwise adding 0.1mL of ammonia water solution, and stirring for reaction for 120min to obtain the phenolic resin coated silicon-based composite material; adding 500 mu L of aniline and 0.25g of ferric trichloride oxidant into the phenolic resin coated silicon-based composite material, stirring at the speed of 300 r/min at the temperature of 40 ℃, and stirring for 3 hours to obtain the poly-backaniline/phenolic resin coated silicon-based composite material; then adding 0.5mL of phosphoric acid solution, stirring for 30min to remove part of phenolic resin, filtering and drying to obtain a silicon-carbon composite material intermediate with a core-shell structure; and (3) putting the core-shell structure silicon-carbon composite material intermediate into a tubular furnace for heat treatment, heating to 750 ℃ at the heating rate of 1 ℃/min in the nitrogen atmosphere, preserving the heat for 3h, and cooling to room temperature to obtain the core-shell structure silicon-carbon composite material for the lithium ion battery.
Example 3
Adding 0.5gSi nano particles (50-150 nm) and 0.5g of SiO particles (2 microns) into 500mL of water, stirring for 3h to uniformly disperse the nano particles in the water solution, adding 250mg of phloroglucinol and 0.25mL of acetaldehyde solution into the solution, dropwise adding 0.15mL of ammonia water solution, and stirring for reacting for 90min to obtain the phenolic resin coated silicon-based composite material; adding 400 mu L of dopamine and 0.25g of ferric nitrate oxidant into the phenolic resin coated silicon-based composite material, stirring at the speed of 650 rpm at 25 ℃, and stirring for 5 hours to obtain a polydopamine/phenolic resin coated silicon-based composite material; adding 1.5mL of sulfuric acid solution, stirring for 30min to remove part of phenolic resin, filtering and drying to obtain a silicon-carbon composite material intermediate with a core-shell structure; and (3) putting the core-shell structure silicon-carbon composite material intermediate into a tubular furnace for heat treatment, heating to 750 ℃ at a heating rate of 2 ℃/min under the argon atmosphere, preserving the heat for 5 hours, and cooling to room temperature to obtain the core-shell structure silicon-carbon composite material for the lithium ion battery.
Example 4
Adding 0.2gSi nano particles (50-150 nm) and 0.8g of SiO particles (2 microns) into 500mL of water, stirring for 3h to uniformly disperse the nano particles in the water solution, adding 500mg of 2-aminophenol and 0.5mL of formaldehyde solution into the solution, adding 0.2g of sodium hydroxide, and stirring for reacting for 120min to obtain the phenolic resin coated silicon-based composite material; adding 500 mu L of thiophene and 0.25g of ferric trichloride oxidant into the phenolic resin coated silicon-based composite material, stirring at the speed of 2000 r/min at the temperature of 0 ℃, and stirring for 3 hours to obtain a polythiophene/phenolic resin coated silicon-based composite material; then adding 2.5mL of nitric acid solution, stirring for 30min to remove part of phenolic resin, filtering and drying to obtain a silicon-carbon composite material intermediate with a core-shell structure; and (3) putting the core-shell structure silicon-carbon composite material intermediate into a tubular furnace for heat treatment, heating to 800 ℃ at a heating rate of 3 ℃/min in an ammonia atmosphere, preserving the temperature for 2h, and cooling to room temperature to obtain the core-shell structure silicon-carbon composite material for the lithium ion battery.
Example 5
Adding 1gSi porous silicon particles (1 mu m) into 500mL of water, stirring for 3h to uniformly disperse the porous silicon particles in an aqueous solution, adding 500mg of 4-aminophenol and 0.5mL of formaldehyde solution into the solution, dropwise adding 0.25mL of ammonia water solution, and stirring for reacting for 60min to obtain the phenolic resin coated silicon-based composite material; adding 100 mu L of 3, 4-ethylenedioxythiophene and 0.25g of ammonium persulfate oxidant into the phenolic resin coated silicon-based composite material, stirring at the speed of 500 r/min at the temperature of 30 ℃, and stirring for 3h to obtain the poly-3, 4-ethylenedioxythiophene/phenolic resin coated silicon-based composite material; adding 2mL of acetic acid solution, stirring for 30min to remove part of phenolic resin, filtering and drying to obtain a silicon-carbon composite material intermediate with a core-shell structure; and (3) putting the core-shell structure silicon-carbon composite material intermediate into a tubular furnace for heat treatment, heating to 950 ℃ at the heating rate of 10 ℃/min under the hydrogen-argon mixed atmosphere, preserving heat for 5h, and cooling to room temperature to obtain the core-shell structure silicon-carbon composite material for the lithium ion battery.
Example 6
Mixing 0.5gSi nano particles (50-150 nm) and 0.5gSiO2Adding particles (1 mu m) into 500mL of water, stirring for 3h to uniformly disperse the particles in the water solution, adding 250mg of 2, 3-diaminophenol and 0.25mL of furfural solution into the solution, adding 0.15g of sodium hydroxide, and stirring for reacting for 120min to obtain the phenolic resin coated silicon-based composite material; adding 200 mu L of pyrrole and 0.25g of ammonium persulfate oxidant into the phenolic resin coated silicon-based composite material, stirring at the speed of 600 revolutions per minute at the temperature of 55 ℃, and stirring for 3 hours to obtain the polypyrrole/phenolic resin coated silicon-based composite material; adding 5mL of citric acid solution, stirring for 60min to remove part of phenolic resin, filtering and drying to obtain a silicon-carbon composite material intermediate with a core-shell structure; and (3) putting the core-shell structure silicon-carbon composite material intermediate into a tubular furnace for heat treatment, heating to 1000 ℃ at a heating rate of 5 ℃/min in a helium atmosphere, preserving heat for 2h, and cooling to room temperature to obtain the core-shell structure silicon-carbon composite material for the lithium ion battery.
As shown in fig. 1, the core-shell structure silicon-carbon composite material for the lithium ion battery prepared in embodiments 1 to 6 is a core-shell structure, and the core-shell structure includes a silicon-based core 1, a first carbon coating layer 2 coated on the surface of the silicon-based core 1, and a second carbon coating layer 3 coated outside the first carbon coating layer 2; the second carbon coating layer 3 has mesopores on the surface, the first carbon coating layer 2 and the second carbon coating layerA cavity 4 is arranged between the carbon coating layers 3; the silicon-based core 1 is SiOxX is in the range of 0 to 2, SiOxOne or more selected from simple substance silicon, silicon monoxide and silicon dioxide; the core-shell structure silicon-carbon composite material for the lithium ion battery can be applied to a lithium battery cathode. As shown in fig. 2, the XRD spectrum of the core-shell structure silicon-carbon composite material for lithium ion batteries prepared in example 1 shows that the main XRD diffraction peak is the diffraction peak of silicon; as shown in FIG. 3, the negative electrode made of the core-shell structure Si-C composite material for lithium ion battery prepared in example 2 was coated with 0.5Ag-1The current density is charged and discharged, and after 500 times of circulation, the capacity is still kept at 2297mAhg-1The coulombic efficiency remained at 98.5%.
With reference to embodiments 1 to 6, the preparation method of the core-shell structure silicon-carbon composite material for the lithium ion battery, disclosed by the invention, is an improvement on the existing method of the core-shell structure silicon-carbon negative electrode material, and the core-shell structure silicon-carbon composite material for the lithium ion battery, prepared by the invention, effectively improves the electrochemical performance of the lithium ion battery; the preparation method comprises the step of coating SiO by polymerizing phenolic aldehyde and polymer monomersxThe silicon-carbon composite material with the core-shell structure for the lithium ion battery is obtained through acid treatment and heat treatment, and the carbon coating layer of the silicon-carbon composite material with the core-shell structure for the lithium ion battery has a mesoporous aperture (the aperture is 2-50 nm), so that a rich and rapid channel is provided for acid treatment, a part of phenolic resin is conveniently removed, a cavity is reserved, and the problem of volume expansion of a silicon-based material is effectively solved; the silicon-carbon composite material with the core-shell structure for the lithium ion battery has high conductivity, and a large amount of doping elements such as N, S and the like are introduced into a carbon coating layer of the silicon-carbon composite material with the core-shell structure 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 is improved, a stable SEI film (solid electrolyte interface film) can be formed, the coulombic efficiency is improved, and the cycle performance of an electrode material is improved; the preparation method of the core-shell structure silicon-carbon composite material for the lithium ion battery is simple and convenient in process, can be freely compounded with graphite, and is 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 (10)

1. The core-shell structure silicon-carbon composite material for the lithium ion battery is characterized by being of a core-shell structure and comprising a silicon-based core, a first carbon coating layer and a second carbon coating layer, wherein the first carbon coating layer is coated on the surface of the silicon-based core, and the second carbon coating layer is coated outside the first carbon coating layer; the surface of the second carbon cladding layer is provided with mesopores, and a cavity is arranged between the second carbon cladding layer and the second carbon cladding layer.
2. The silicon-carbon composite material with the core-shell structure for the lithium ion battery of claim 1, wherein the silicon-based inner core is SiOxX ranges from 0, 1, 2; the SiOxOne or more selected from elemental silicon, silicon monoxide and silicon dioxide.
3. A negative electrode comprising the core-shell structure silicon-carbon composite material for a lithium ion battery according to claim 1 or 2.
4. A preparation method of a core-shell structure silicon-carbon composite material for a lithium ion battery is characterized in that phenol, aldehyde and a polymer monomer are adopted to coat SiOxAnd then preparing the core-shell structure silicon-carbon composite material for the lithium ion battery according to claim 1 or 2 by acid treatment and heat treatment.
5. The method of claim 4, comprising the steps of:
s1, mixing SiOxUniformly dispersing the aqueous solution, adding phenol and aldehyde, and stirring to obtain the phenolic resin coated silicon-based composite material;
s2, adding a polymer monomer and an oxidant into the phenolic resin coated silicon-based composite material, and carrying out polymerization reaction to obtain a polymer/phenolic resin coated silicon-based composite material with mesopores;
s3, adding acid into the polymer/phenolic resin coated silicon-based composite material for acid treatment, removing the phenolic resin in the mesopores, and filtering and drying to obtain a silicon-carbon composite material intermediate with a core-shell structure;
and S4, performing heat treatment on the core-shell structure silicon-carbon composite material intermediate to obtain the core-shell structure silicon-carbon composite material for the lithium ion battery.
6. The method according to claim 5, wherein in step S1, the SiO isxThe particle size of (A) is 1 nm-50 μm.
7. The method according to claim 5, wherein in step S1, the phenol is one selected from the group consisting of phenol, cresol, xylenol, resorcinol, phloroglucinol, hydroquinone, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2, 3-diaminophenol, 2, 4-diaminophenol, 4-nitro-2-aminophenol, 5-nitro-2-aminophenol, 6-nitro-2-aminophenol, 4, 6-dinitro-2-aminophenol, 2-nitro-4-aminophenol, 5-nitro-2-aminophenol, 3-nitro-4-aminophenol, 4-sulfonamide-2-aminophenol, and/or
In the step S1, the aldehyde is selected from one of formaldehyde, paraformaldehyde, trioxymethylene, acetaldehyde and furfural, and/or
In the step S2, the polymer monomer is selected from one or more of pyrrole, aniline, thiophene, 3-methoxythiophene, 3, 4-ethylenedioxythiophene, and dopamine, and/or
In step S3, the acid is selected from one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, formic acid, and citric acid.
8. The method according to claim 5, wherein in step S2, the polymerization reaction temperature is 0-80 ℃, the reaction time is 0.1-12 h, and the polymerization reaction condition is stirring or ultrasound.
9. The method of claim 8, wherein the stirring rate is 100 to 2000 rpm.
10. The method according to claim 5, wherein in the step S4, the temperature is 600-1000 ℃, the temperature rising rate is 1-10 ℃/min, the reaction time is 0.5-6 h, and the atmosphere is one or more selected from carbon dioxide, argon, nitrogen, helium, ammonia, hydrogen and vacuum.
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