CN113540422A - Silicon-carbon shell nano composite material, preparation method and lithium ion battery electrode - Google Patents

Silicon-carbon shell nano composite material, preparation method and lithium ion battery electrode Download PDF

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CN113540422A
CN113540422A CN202110796119.4A CN202110796119A CN113540422A CN 113540422 A CN113540422 A CN 113540422A CN 202110796119 A CN202110796119 A CN 202110796119A CN 113540422 A CN113540422 A CN 113540422A
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silicon
mixed solution
carbon shell
oxide
shell
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CN113540422B (en
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王德利
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Luhua Zhifu Electronics Shenzhen Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a silicon-carbon shell nano composite material, which comprises a plurality of silicon-carbon shell nano particles, wherein the silicon-carbon shell nano particles comprise: the device comprises a shell structure and a plurality of filling particles, wherein the shell structure is a hollow structure formed by graphene materials, and the size of the shell structure is 100 nanometers to 100 micrometers; a plurality of filler particles are composed of a silicon nanomaterial and are disposed within the shell structure, the filler particles having a size in the range of 5 nanometers to 500 nanometers. The invention also provides a preparation method of the silicon-carbon shell nano composite material and a corresponding lithium ion battery electrode.

Description

Silicon-carbon shell nano composite material, preparation method and lithium ion battery electrode
Technical Field
The invention relates to the field of batteries, in particular to a silicon-carbon shell nano composite material, a manufacturing method and a lithium ion battery electrode.
Background
With the increasing popularization of wearable devices and the rapid popularization of industrial internet, the charged battery industry faces unprecedented opportunities and challenges due to the wide demand of remote medical treatment for portable medical detection and treatment devices for new crown epidemic situations and the rapid development of 5G communication technology and edge computing.
The lithium ion battery has the advantages of high voltage, high energy density, light weight, small volume, long cycle life, no memory effect, good environmental benefit and the like. The negative electrode material is a key factor for determining reversible capacity and cycle life of lithium ions.
The insertion compound formed by lithium and graphitized carbon material has a potential different from that of metallic lithium by less than 0.5V and has excellent cycle performance, so that the insertion compound can replace the metallic lithium to be used as a negative electrode of a lithium ion rechargeable battery.
However, the existing silicon carbon compound material has poor stability and high preparation difficulty, so that the manufacturing cost of the existing lithium ion battery electrode and electrode material is high. Therefore, it is necessary to provide a silicon-carbon shell nanocomposite, a manufacturing method thereof and a lithium ion battery electrode to solve the technical problems.
Disclosure of Invention
The invention provides a silicon-carbon shell nano composite material, a manufacturing method and a lithium ion battery electrode, and aims to solve the technical problem that the manufacturing cost of the conventional lithium ion battery electrode and electrode material is high.
The embodiment of the invention provides a silicon-carbon shell nano composite material which comprises a plurality of silicon-carbon shell nano particles, wherein the silicon-carbon shell nano particles comprise:
the shell structure is a hollow structure made of graphene materials, and the size of the shell structure is 100 nanometers to 100 micrometers;
a plurality of filler particles composed of a silicon nanomaterial disposed within the shell structure, the filler particles having a size of 5 nanometers to 500 nanometers.
The silicon-carbon shell nanocomposite material of the invention, wherein the size of the shell structure is 5 microns to 100 microns; the filler particles have a size of 50 nm to 200 nm.
The embodiment of the invention also provides a preparation method of the silicon-carbon shell nano composite material, which comprises the following steps:
mixing silicon nanoparticles, carboxylated graphene, and aminated graphene in water to form a material mixture;
adding an acidic solution or an alkaline solution into the material mixed solution to enable the pH value of the material mixed solution to be a set value, so as to obtain a material self-assembly mixed solution;
standing the material self-assembly mixed solution for a set time to form a silicon-carbon shell nano mixed solution;
and filtering and drying the silicon-carbon shell-shell nano mixed solution to obtain the silicon-carbon shell-shell nano particles.
In the method for manufacturing the silicon-carbon shell nanocomposite material, the step of adding the acidic solution or the alkaline solution to the material mixed solution to make the pH value of the material mixed solution a set value so as to obtain the material self-assembly mixed solution specifically comprises the following steps:
and adding a hydrochloric acid solution or a sodium hydroxide solution into the material mixed solution to enable the pH value of the material mixed solution to be 7-9, thereby obtaining the material self-assembly mixed solution.
In the method for preparing the silicon-carbon shell-shell nano composite material, the step of standing the material self-assembly mixed solution for a set time to form the silicon-carbon shell-shell nano mixed solution specifically comprises the following steps:
and standing the material self-assembly mixed solution for 5-60 minutes to form the silicon-carbon shell nano mixed solution.
In the preparation method of the silicon-carbon shell nano composite material, the carboxylated graphene and the aminated graphene in the silicon-carbon shell nano mixed solution are self-assembled based on ionic bonds to form the silicon-carbon shell nano particles wrapping the silicon nano particles.
The embodiment of the invention also provides a preparation method of the silicon-carbon shell nano composite material, which comprises the following steps:
mixing silicon nanoparticles, carboxylated graphene oxide, and aminated graphene oxide in water to form a first oxidation material mixture;
adding an acidic solution or an alkaline solution into the first oxide material mixed solution to enable the pH value of the first oxide material mixed solution to be 7-9, so as to obtain a first oxide material self-assembly mixed solution;
standing the first oxide material self-assembly mixed solution for 5-60 minutes to form a first silicon oxide carbon shell nano mixed solution; wherein the carboxylated graphene oxide and the aminated graphene oxide in the first SiO carbon shell-shell nano mixed solution are self-assembled based on ionic bonds to form first SiO carbon shell-nanoparticles encapsulating the silicon nanoparticles;
filtering and drying the first SiO carbon shell-shell nano mixed solution to obtain first SiO carbon shell-shell nano particles;
and carrying out high-temperature treatment on the first carbon monoxide shell nano particles in a nitrogen or helium environment so as to reduce graphene oxide in the first carbon monoxide shell nano particles into graphene, and further obtaining the carbon monoxide shell nano particles.
The embodiment of the invention also provides a preparation method of the silicon-carbon shell nano composite material, which comprises the following steps:
mixing silicon oxide nanoparticles, carboxylated graphene, and aminated graphene in water to form a second oxide material mixture;
adding an acidic solution or an alkaline solution into the second oxide material mixed solution to enable the pH value of the second oxide material mixed solution to be 7-9, so as to obtain a second oxide material self-assembly mixed solution;
standing the self-assembly mixed solution of the second oxide material for 5-60 minutes to form a carbon shell nano mixed solution of second silicon dioxide; wherein the carboxylated graphene and the aminated graphene in the second silica carbon shell-nanoparticle mixed liquor are self-assembled based on ionic bonds to form second silica carbon shell-nanoparticles encapsulating the silica nanoparticles;
filtering and drying the second silica carbon shell nano mixed solution to obtain second silica carbon shell nano particles;
and carrying out electrochemical reduction reaction on the second silicon dioxide carbon shell nano particles to reduce the silicon oxide nano particles in the second silicon dioxide carbon shell nano particles into silicon nano particles, thereby obtaining the silicon carbon shell nano particles.
The embodiment of the invention also provides a preparation method of the silicon-carbon shell nano composite material, which comprises the following steps:
mixing silicon oxide nanoparticles, carboxylated graphene oxide and aminated graphene oxide in water to form a third oxide material mixed solution;
adding an acidic solution or an alkaline solution into the third oxide material mixed solution to enable the pH value of the third oxide material mixed solution to be 7-9, so as to obtain a third oxide material self-assembly mixed solution;
standing the self-assembly mixed solution of the third oxide material for 5-60 minutes to form a nano mixed solution of the third silicon oxide and the carbon shell; wherein the carboxylated graphene oxide and the aminated graphene oxide in the third silica carbon shell nano mixed solution are self-assembled based on ionic bonds to form third silica carbon shell nano particles wrapping the silica nano particles;
filtering and drying the third silica carbon shell nano mixed solution to obtain third silica carbon shell nano particles;
performing electrochemical reduction reaction on the third silicon oxide carbon shell nanoparticles to reduce the silicon oxide nanoparticles in the third silicon oxide carbon shell nanoparticles into silicon nanoparticles; and then carrying out high-temperature treatment on the third silicon oxide carbon shell nano particles in a nitrogen or helium environment so as to reduce the graphene oxide in the third silicon oxide carbon shell nano particles into graphene, thereby obtaining the silicon carbon shell nano particles.
The embodiment of the invention also provides a lithium ion battery electrode made of the silicon-carbon shell nanocomposite.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the silicon-carbon shell nano-particles are formed on the basis of the shell structure formed by graphene and the filling particles formed by the silicon nano-material, so that the preparation difficulty of the silicon-carbon compound material is reduced, and the manufacturing cost of the lithium ion battery electrode and the electrode material is reduced; the technical problem that the manufacturing cost of the conventional lithium ion battery electrode and electrode materials is high is effectively solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments are briefly introduced below, and the drawings in the following description are only corresponding to some embodiments of the present invention.
FIG. 1 is a schematic structural diagram of an embodiment of a silicon carbon shell nanocomposite material of the present invention;
FIG. 2A is a flow chart of a first embodiment of a method of making a silicon carbon shell nanocomposite of the invention;
fig. 2B is a schematic diagram of the formation process of carboxylated (oxidized) graphene and aminated (oxidized) graphene according to the present invention;
fig. 2C is a schematic view of ionic bond self-assembly of carboxylated graphene and aminated graphene according to the present invention;
FIG. 3 is a flow chart of a second embodiment of the method of making a silicon carbon shell nanocomposite material of the invention;
FIG. 4 is a flow chart of a third embodiment of the method of making a silicon carbon shell nanocomposite material of the invention;
FIG. 5 is a flow chart of a fourth embodiment of the method of making a silicon carbon shell nanocomposite of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, fig. 1 is a schematic structural diagram of an embodiment of a silicon-carbon shell nanocomposite material of the present invention. The embodiment of the invention provides a silicon-carbon shell-shell nano composite material, which comprises a plurality of silicon-carbon shell-shell nano particles, wherein the silicon-carbon shell-shell nano particles 10 comprise a shell structure 11 and a plurality of filling particles 12.
The shell structure 11 is a hollow structure made of graphene materials, and the size of the shell structure 11 is 100 nanometers to 100 micrometers; the filler particles 12 are composed of a silicon nanomaterial and are disposed within the shell structure 11, and the size of the filler particles 12 is 5 nm to 500 nm.
The silicon-carbon shell nanocomposite can greatly increase the electronic conductivity inside the electrode through the network formed by the graphene, reduce the internal resistance of the electrode, reduce internal consumption and heat caused by charging and discharging, and increase the charging and discharging times of the corresponding battery and the service life of the battery.
Preferably, when the size of the shell structure 11 of the silicon carbon shell nanoparticle 10 is 5 micrometers to 50 micrometers and the size of the filler particle 12 is 50 nanometers to 200 nanometers, the corresponding silicon carbon shell nanocomposite has better electrochemical and mechanical properties.
Referring to fig. 2A, fig. 2A is a flow chart of a method for manufacturing a silicon-carbon shell nanocomposite material according to a first embodiment of the present invention.
The preparation method of the silicon-carbon shell nano composite material comprises the following steps:
step S201, mixing silicon nanoparticles, carboxylated graphene, and aminated graphene in water to form a material mixture;
step S202, adding an acidic solution or an alkaline solution into the material mixed solution to enable the pH value of the material mixed solution to be a set value, and thus obtaining a material self-assembly mixed solution;
step S203, standing the material self-assembly mixed solution for a set time to form a silicon-carbon shell nano mixed solution;
and step S204, filtering and drying the silicon-carbon shell nano mixed solution to obtain the silicon-carbon shell nano particles.
The detailed flow of the method for preparing the silicon-carbon shell nanocomposite material of the present embodiment is described in detail below.
In step S201, performing carboxylation on graphene to obtain carboxylated graphene, and performing amination on graphene to obtain aminated graphene; for a specific process of forming carboxylated graphene and aminated graphene, please refer to fig. 2B.
And then mixing the silicon nanoparticles, the carboxylic acid graphene and the aminated graphene in water according to the x/y/z ratio to obtain a material mixed solution. x/y/z is a molar ratio, x is 5-50, y is 0.95-1.05, z is 1; y/z is determined according to the number of carboxyl groups on the carboxylated graphene and the number of amino groups of the aminated graphene.
In step S202, a hydrochloric acid solution or a sodium hydroxide solution is added to the material mixture solution so that the pH of the material mixture solution is 7 to 9, thereby obtaining a material self-assembly mixture solution.
Therefore, when the pH value of the material mixed liquid is 7-9, the carboxylic acid group and the amino group on the graphene can be ionized to form COO-Negative ions and NH3 +A positive ion.
In step S203, the material self-assembly mixed solution is allowed to stand for 5 to 60 minutes, and the carboxylated graphene and the graphene amide are self-assembled based on ionic bonds to form silicon-carbon shell nanoparticles wrapping the silicon nanoparticles, and then the material self-assembly mixed solution is converted into a silicon-carbon shell nanoparticle mixed solution.
The chemical formula of the ionic bond self-assembly is as follows:
R1-COOH→R1-COO-+H+；
R2-NH2+H+→R2-NH3 +；
R1-COO-+R2-NH3 +→R1-COO-NH3 +-R2；
n R1-COO-+mR2-NH3 +→(m/n)R1-COO-NH3 +-R2；
wherein R is1Being a carboxylic acid graphene, R2Is aminated graphene; n/m is a molar ratio, which is determined according to the number of carboxyl groups on the carboxylated graphene and the number of amino groups of the aminated graphene; may be 1: 1. Please refer to fig. 2C for a specific self-assembly process.
In step S204, the silicon-carbon shell-nano mixed solution obtained in step S203 is filtered and dried to obtain silicon-carbon shell-nano particles.
Thus, the process of fabricating the silicon-carbon shell nanocomposite material of the present example is completed.
The method for preparing the silicon-carbon shell-nano composite material of the embodiment forms the silicon-carbon shell-nano particles based on the shell structure formed by the graphene and the filling particles formed by the silicon nano material, thereby reducing the preparation difficulty of the silicon-carbon compound material and reducing the preparation cost of the lithium ion battery electrode and the electrode material.
Referring to fig. 3, fig. 3 is a flow chart of a method for manufacturing a silicon-carbon shell nanocomposite material according to a second embodiment of the present invention. The preparation method of the silicon-carbon shell nano composite material comprises the following steps:
step S301, mixing silicon nanoparticles, carboxylated graphene oxide and aminated graphene oxide in water to form a first oxidation material mixed solution;
step S302, adding an acidic solution or an alkaline solution into the first oxidizing material mixed solution to enable the pH value of the first oxidizing material mixed solution to be 7-9, and thus obtaining a first oxidizing material self-assembly mixed solution;
step S303, standing the first oxide material self-assembly mixed solution for 5-60 minutes to form a first silicon oxide carbon shell nano mixed solution; the carboxylic graphene oxide and the amination graphene oxide in the first silicon oxide carbon shell nano mixed solution are self-assembled based on ionic bonds to form first silicon oxide carbon shell nano particles wrapping silicon nano particles;
step S304, filtering and drying the first carbon monoxide shell and shell nano mixed solution to obtain first carbon monoxide shell and shell nano particles;
step S305, performing high-temperature treatment on the first carbon monoxide shell nanoparticles in a nitrogen or helium environment to reduce graphene oxide in the first carbon monoxide shell nanoparticles into graphene, and further obtaining the carbon monoxide shell nanoparticles.
The detailed flow of the method for preparing the silicon-carbon shell nanocomposite material of the present embodiment is described in detail below.
In step S301, graphene oxide may be prepared by using potassium permanganate and hydrogen peroxide through a one-step method, and then carboxylic acid group is performed on the graphene oxide to obtain carboxylated graphene oxide, and in addition, the graphene oxide is aminated to obtain aminated graphene oxide, and for a specific formation process of the carboxylated graphene oxide and the aminated graphene oxide, please refer to fig. 2B.
And then mixing the silicon nanoparticles, the carboxylated graphene oxide and the aminated graphene oxide in water according to the x/y/z ratio to obtain a first oxidation material mixed solution. x/y/z is a molar ratio, x is 5-50, y is 0.95-1.05, z is 1; y/z is determined by the number of carboxyl groups on the carboxylated graphene oxide and the number of amino groups on the aminated graphene oxide.
In step S302, a hydrochloric acid solution or a sodium hydroxide solution is added to the first oxidizing material mixed solution so that the first oxidizing material mixed solution has a pH of 7 to 9, thereby obtaining a first oxidizing material self-assembled mixed solution.
Therefore, when the pH value of the first oxide material self-assembly mixed solution is 7-9, the carboxylic acid group and the amino group on the graphene oxide are ionized to form COO-Negative ions and NH3 +A positive ion.
In step S303, the first oxidation material self-assembly mixed solution is allowed to stand for 5 to 60 minutes, the carboxylated graphene oxide and the aminated graphene oxide are self-assembled based on ionic bonds, to form first carbon monoxide shell nanoparticles wrapping the silicon nanoparticles, and the first oxidation material self-assembly mixed solution is converted into the first carbon monoxide shell nanoparticle mixed solution.
In step S304, the first sio-carbon shell-shell nano-mixed solution obtained in step S303 is filtered and dried to obtain first sio-carbon shell-shell nano-particles.
In step S305, in a nitrogen or helium environment, performing high temperature treatment on the first sio-carbon shell nanoparticles at an environment of 900-1250 degrees to reduce graphene oxide in the first sio-carbon shell nanoparticles to graphene, thereby obtaining the sio-carbon shell nanoparticles.
Thus, the process of fabricating the silicon-carbon shell nanocomposite material of the present example is completed.
On the basis of the first embodiment, the method for manufacturing the silicon-carbon shell nanocomposite material forms the silicon-carbon shell nanoparticles based on the shell structure formed by the graphene oxide and the filling particles formed by the silicon nanomaterial, the graphene has better stability, the difficulty in preparing the silicon-carbon compound material is effectively reduced, and the manufacturing cost of the lithium ion battery electrode and the electrode material is reduced.
Referring to fig. 4, fig. 4 is a flowchart illustrating a method for fabricating a silicon carbon shell nanocomposite material according to a third embodiment of the present invention. The preparation method of the silicon-carbon shell nano composite material comprises the following steps:
step S401, mixing silicon oxide nanoparticles, graphene carboxylate and aminated graphene in water to form a second oxide material mixed solution;
step S402, adding an acidic solution or an alkaline solution into the second oxide material mixed solution to enable the pH value of the second oxide material mixed solution to be 7-9, and thus obtaining a second oxide material self-assembly mixed solution;
step S403, standing the self-assembly mixed solution of the second oxide material for 5-60 minutes to form a carbon shell and shell nano mixed solution of the second oxide material; wherein the carboxyl graphene and the amino graphene in the second silica carbon shell nano mixed solution are self-assembled based on ionic bonds to form second silica carbon shell nano particles wrapping the silica nano particles;
step S404, filtering and drying the second silicon dioxide carbon shell nano mixed solution to obtain second silicon dioxide carbon shell nano particles;
step S405, performing electrochemical reduction reaction on the second silicon dioxide carbon shell nano particles to reduce the silicon dioxide nano particles in the second silicon dioxide carbon shell nano particles into silicon nano particles, thereby obtaining the silicon carbon shell nano particles.
The detailed flow of the method for preparing the silicon-carbon shell nanocomposite material of the present embodiment is described in detail below.
In step S401, silicon oxide nanoparticles are synthesized by using a chemical sol-gel method, and the carboxylated graphene is obtained by carboxylating the graphene, and the aminated graphene is obtained by amination of the graphene; for a specific process of forming carboxylated graphene and aminated graphene, please refer to fig. 2B.
And then mixing the silicon oxide nanoparticles, the carboxylic graphene and the aminated graphene in water according to the x/y/z ratio to obtain a second oxide material mixed solution. x/y/z is a molar ratio, x is 5-50, y is 0.95-1.05, z is 1; y/z is determined by the number of carboxyl groups on the carboxylated graphene oxide and the number of amino groups on the aminated graphene oxide.
In step S402, a hydrochloric acid solution or a sodium hydroxide solution is added to the second oxide material mixed solution so that the pH of the second oxide material mixed solution is 7 to 9, thereby obtaining a second oxide material self-assembled mixed solution.
Therefore, when the pH value of the second oxide material self-assembly mixed solution is 7-9, the carboxylic acid group and the amino group on the graphene can be ionized to form COO-Negative ions and NH3 +A positive ion.
In step S403, the second oxide material self-assembly mixed solution is allowed to stand for 5 to 60 minutes, and the carboxylated graphene and the aminated graphene are self-assembled based on ionic bonds to form second silica carbon shell nanoparticles wrapping the silica nanoparticles, and then the second oxide material self-assembly mixed solution is converted into the second silica carbon shell nanoparticle mixed solution.
In step S404, the second silica carbon shell-nanoparticle mixture obtained in step S403 is filtered and dried to obtain second silica carbon shell-nanoparticle.
In step S405, CaCl is used2And performing electrochemical reduction reaction on the second silicon dioxide carbon shell nano particles by using the solvent to reduce the silicon oxide nano particles in the second silicon dioxide carbon shell nano particles into silicon nano particles, thereby obtaining the silicon carbon shell nano particles.
Thus, the process of fabricating the silicon-carbon shell nanocomposite material of the present example is completed.
On the basis of the first embodiment, the method for manufacturing the silicon-carbon shell nanocomposite material forms the silicon-carbon shell nanoparticles based on the shell structure formed by the graphene and the filling particles formed by the silicon oxide nanomaterial, the silicon nanomaterial has better stability, the difficulty in preparing the silicon-carbon compound material is effectively reduced, and the manufacturing cost of the lithium ion battery electrode and the electrode material is reduced.
Referring to fig. 5, fig. 5 is a flowchart illustrating a method for manufacturing a silicon-carbon shell nanocomposite material according to a fourth embodiment of the present invention. The preparation method of the silicon-carbon shell nano composite material comprises the following steps:
step S501, mixing silicon oxide nanoparticles, carboxylated graphene oxide and aminated graphene oxide in water to form a third oxide material mixed solution;
step S502, adding an acidic solution or an alkaline solution into the third oxide material mixed solution to enable the pH value of the third oxide material mixed solution to be 7-9, so as to obtain a third oxide material self-assembly mixed solution;
step S503, standing the third oxide material self-assembly mixed solution for 5-60 minutes to form a third silicon oxide carbon shell nano mixed solution; wherein the carboxylated graphene oxide and the aminated graphene oxide in the third silicon oxide carbon shell nano mixed solution are self-assembled based on ionic bonds to form third silicon oxide carbon shell nano particles wrapping the silicon oxide nano particles;
step S504, filtering and drying the third silicon oxide carbon shell nano mixed solution to obtain third silicon oxide carbon shell nano particles;
step S505, performing electrochemical reduction reaction on the third silicon oxide carbon shell nano particles to reduce the silicon oxide nano particles in the third silicon oxide carbon shell nano particles into silicon nano particles; and then carrying out high-temperature treatment on the third silicon oxide carbon shell nano particles in a nitrogen or helium environment so as to reduce the graphene oxide in the third silicon oxide carbon shell nano particles into graphene, thereby obtaining the silicon carbon shell nano particles.
The detailed flow of the method for preparing the silicon-carbon shell nanocomposite material of the present embodiment is described in detail below.
In step S501, silicon oxide nanoparticles are synthesized by a chemical sol-gel method, graphene oxide can be prepared by a one-step method using potassium permanganate and hydrogen peroxide, then carboxylic acid group is performed on the graphene oxide to obtain carboxylated graphene oxide, and the graphene oxide is aminated to obtain aminated graphene oxide, and for a specific formation process of the carboxylated graphene oxide and the aminated graphene oxide, see fig. 2B.
And then mixing the silicon oxide nanoparticles, the carboxylic acid graphene oxide and the amination graphene oxide in water according to the x/y/z ratio to obtain a third oxide material mixed solution. x/y/z is a molar ratio, x is 5-50, y is 0.95-1.05, z is 1; y/z is determined by the number of carboxyl groups on the carboxylated graphene oxide and the number of amino groups on the aminated graphene oxide.
In step S502, a hydrochloric acid solution or a sodium hydroxide solution is added to the third oxide material mixed solution to adjust the pH of the third oxide material mixed solution to 7 to 9, thereby obtaining a third oxide material self-assembly mixed solution.
Therefore, when the pH value of the third oxide material self-assembly mixed solution is 7-9, the carboxylic acid group and the amino group on the graphene oxide can be ionized to form COO-Negative ions and NH3 +A positive ion.
In step S503, the third oxide material self-assembly mixed solution is allowed to stand for 5 to 60 minutes, and the carboxylic acid oxidized graphene and the amino oxidized graphene are self-assembled based on ionic bonds to form third oxide carbon shell nanoparticles wrapping the silicon oxide nanoparticles, and then the third oxide material self-assembly mixed solution is converted into a third oxide carbon shell nanoparticle mixed solution.
In step S504, the third silica carbon shell-nanoparticle mixed solution obtained in step S503 is filtered and dried to obtain third silica carbon shell-nanoparticle.
In step S505, CaCl is used2Carrying out electrochemical reduction reaction on the second silicon dioxide carbon shell nano particles by using the solvent so as to reduce the silicon oxide nano particles in the third silicon oxide carbon shell nano particles into silicon nano particles; and in a nitrogen or helium environment, performing high-temperature treatment on the third silicon oxide carbon shell nano particles in an environment of 900-1250 ℃ to reduce graphene oxide in the third silicon oxide carbon shell nano particles into graphene, thereby obtaining the silicon carbon shell nano particles.
Thus, the process of fabricating the silicon-carbon shell nanocomposite material of the present example is completed.
On the basis of the first embodiment, the method for manufacturing the silicon-carbon shell nanocomposite material forms the silicon-carbon shell nanoparticles based on the shell structure formed by the graphene oxide and the filling particles formed by the silicon oxide nanomaterial, the graphene material and the silicon nanomaterial have better stability, the difficulty in preparing the silicon-carbon compound material is effectively reduced, and the manufacturing cost of the lithium ion battery electrode and the electrode material is reduced.
The invention also provides a lithium ion battery electrode manufactured by using the silicon-carbon shell-shell nano composite material, wherein the silicon-carbon shell-shell nano composite material comprises a plurality of silicon-carbon shell-shell nano particles, and the silicon-carbon shell-shell nano particles comprise a shell structure and a plurality of filling particles.
The shell structure is a hollow structure formed by graphene materials, and the size of the shell structure is 100 nanometers to 100 micrometers; the filling particles are made of silicon nano materials and arranged in the shell structure, and the size of the filling particles is 5-500 nanometers. Preferably, the shell structure has a size of 5 to 50 microns and the filler particles have a size of 50 to 200 nanometers.
The lithium ion battery electrode made of the silicon-carbon shell nano composite material has better electrochemical and mechanical properties.
According to the silicon-carbon shell nano composite material and the lithium ion battery electrode, the silicon-carbon shell nano particles are formed on the basis of the shell structure formed by graphene and the filling particles formed by the silicon nano material, so that the preparation difficulty of the silicon-carbon compound material is reduced, and the manufacturing cost of the lithium ion battery electrode and the electrode material is reduced; the technical problem that the manufacturing cost of the conventional lithium ion battery electrode and electrode materials is high is effectively solved.
In summary, although the present invention has been described with reference to the preferred embodiments, the above-described preferred embodiments are not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, therefore, the scope of the present invention shall be determined by the appended claims.

Claims (10)

1. A silicon carbon shell nanocomposite comprising a plurality of silicon carbon shell nanoparticles, wherein the silicon carbon shell nanoparticles comprise:
the shell structure is a hollow structure made of graphene materials, and the size of the shell structure is 100 nanometers to 100 micrometers;
a plurality of filler particles composed of a silicon nanomaterial disposed within the shell structure, the filler particles having a size of 5 nanometers to 500 nanometers.
2. The silicon carbon shell nanocomposite material of claim 1, wherein the shell structure has a size of 5 to 100 microns; the filler particles have a size of 50 nm to 200 nm.
3. A method of making the silicon carbon shell nanocomposite material of claim 1, comprising:
mixing silicon nanoparticles, carboxylated graphene, and aminated graphene in water to form a material mixture;
adding an acidic solution or an alkaline solution into the material mixed solution to enable the pH value of the material mixed solution to be a set value, so as to obtain a material self-assembly mixed solution;
standing the material self-assembly mixed solution for a set time to form a silicon-carbon shell nano mixed solution;
and filtering and drying the silicon-carbon shell-shell nano mixed solution to obtain the silicon-carbon shell-shell nano particles.
4. The method for preparing a silicon-carbon shell nanocomposite material as claimed in claim 3, wherein the step of adding an acidic solution or an alkaline solution to the material mixture to set the pH value of the material mixture to obtain a material self-assembly mixture specifically comprises:
and adding a hydrochloric acid solution or a sodium hydroxide solution into the material mixed solution to enable the pH value of the material mixed solution to be 7-9, thereby obtaining the material self-assembly mixed solution.
5. The method for preparing a silicon-carbon shell-nano composite material according to claim 3, wherein the step of standing the material self-assembly mixed solution for a set time to form the silicon-carbon shell-nano mixed solution comprises the following specific steps:
and standing the material self-assembly mixed solution for 5-60 minutes to form the silicon-carbon shell nano mixed solution.
6. The method of claim 3, wherein the carboxylated graphene and the aminated graphene in the Si-C shell-nano mixed solution are self-assembled based on ionic bonds to form Si-C shell-nano particles encapsulating the Si-C nanoparticles.
7. A method of making the silicon carbon shell nanocomposite material of claim 1, comprising:
mixing silicon nanoparticles, carboxylated graphene oxide, and aminated graphene oxide in water to form a first oxidation material mixture;
adding an acidic solution or an alkaline solution into the first oxide material mixed solution to enable the pH value of the first oxide material mixed solution to be 7-9, so as to obtain a first oxide material self-assembly mixed solution;
standing the first oxide material self-assembly mixed solution for 5-60 minutes to form a first silicon oxide carbon shell nano mixed solution; wherein the carboxylated graphene oxide and the aminated graphene oxide in the first SiO carbon shell-shell nano mixed solution are self-assembled based on ionic bonds to form first SiO carbon shell-nanoparticles encapsulating the silicon nanoparticles;
filtering and drying the first SiO carbon shell-shell nano mixed solution to obtain first SiO carbon shell-shell nano particles;
and carrying out high-temperature treatment on the first carbon monoxide shell nano particles in a nitrogen or helium environment so as to reduce graphene oxide in the first carbon monoxide shell nano particles into graphene, and further obtaining the carbon monoxide shell nano particles.
8. A method of making the silicon carbon shell nanocomposite material of claim 1, comprising:
mixing silicon oxide nanoparticles, carboxylated graphene, and aminated graphene in water to form a second oxide material mixture;
adding an acidic solution or an alkaline solution into the second oxide material mixed solution to enable the pH value of the second oxide material mixed solution to be 7-9, so as to obtain a second oxide material self-assembly mixed solution;
standing the self-assembly mixed solution of the second oxide material for 5-60 minutes to form a carbon shell nano mixed solution of second silicon dioxide; wherein the carboxylated graphene and the aminated graphene in the second silica carbon shell-nanoparticle mixed liquor are self-assembled based on ionic bonds to form second silica carbon shell-nanoparticles encapsulating the silica nanoparticles;
filtering and drying the second silica carbon shell nano mixed solution to obtain second silica carbon shell nano particles;
and carrying out electrochemical reduction reaction on the second silicon dioxide carbon shell nano particles to reduce the silicon oxide nano particles in the second silicon dioxide carbon shell nano particles into silicon nano particles, thereby obtaining the silicon carbon shell nano particles.
9. A method of making the silicon carbon shell nanocomposite material of claim 1, comprising:
mixing silicon oxide nanoparticles, carboxylated graphene oxide and aminated graphene oxide in water to form a third oxide material mixed solution;
adding an acidic solution or an alkaline solution into the third oxide material mixed solution to enable the pH value of the third oxide material mixed solution to be 7-9, so as to obtain a third oxide material self-assembly mixed solution;
standing the self-assembly mixed solution of the third oxide material for 5-60 minutes to form a nano mixed solution of the third silicon oxide and the carbon shell; wherein the carboxylated graphene oxide and the aminated graphene oxide in the third silica carbon shell nano mixed solution are self-assembled based on ionic bonds to form third silica carbon shell nano particles wrapping the silica nano particles;
filtering and drying the third silica carbon shell nano mixed solution to obtain third silica carbon shell nano particles;
performing electrochemical reduction reaction on the third silicon oxide carbon shell nanoparticles to reduce the silicon oxide nanoparticles in the third silicon oxide carbon shell nanoparticles into silicon nanoparticles; and then carrying out high-temperature treatment on the third silicon oxide carbon shell nano particles in a nitrogen or helium environment so as to reduce the graphene oxide in the third silicon oxide carbon shell nano particles into graphene, thereby obtaining the silicon carbon shell nano particles.
10. A lithium ion battery electrode fabricated using the silicon carbon shell nanocomposite of claim 1.
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