CN113839014A - Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery - Google Patents

Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery Download PDF

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CN113839014A
CN113839014A CN202010513230.3A CN202010513230A CN113839014A CN 113839014 A CN113839014 A CN 113839014A CN 202010513230 A CN202010513230 A CN 202010513230A CN 113839014 A CN113839014 A CN 113839014A
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silicon
carbon
negative electrode
source
electrode material
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CN113839014B (en
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孙赛
张丝雨
高焕新
张同宝
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/36—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 relates to the field of lithium ion batteries, and discloses a silicon-carbon negative electrode material, a preparation method and an application thereof, and a lithium ion battery. The preparation method of the silicon-carbon negative electrode material comprises the following steps: (1) mixing a carbon-containing substance with a chain polymer solution, then adding a silicon source into the mixture, and separating the obtained mixture to obtain a solid substance; (2) and blending the solid substance and a carbon source precursor, and then roasting. The silicon-carbon cathode material provided by the invention can improve the dispersibility of nano silicon, relieve the volume expansion of silicon, improve the cycling stability of the material, and can improve the energy density of a lithium battery when being applied to the lithium battery.

Description

Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a silicon-carbon negative electrode material, a preparation method and application thereof and a lithium ion battery.
Background
At present, graphite cathode materials are widely adopted by lithium ion batteries, but the theoretical lithium storage capacity of the graphite cathode materials is only 372mAh/g, so that the requirement of a new product on high power or large capacity of the lithium ion battery cannot be met, and the further development of the capacity of the lithium ion battery is seriously hindered. The theoretical specific capacity of the silicon-based negative electrode material is 4200 mA.h.g-1The material is a negative electrode material with the highest gram capacity at present, but the material is pulverized and secondarily agglomerated due to the fact that large volume change occurs in the subsequent lithium insertion and extraction process, so that active substances are slowly inactivated, the capacity of the material is quickly attenuated, and in addition, close electric contact between a negative electrode piece and a current collector is lost due to the volume change in the lithium insertion and extraction process. Therefore, whether the cycle performance is improved or not becomes a key technology for large-scale commercial application of the silicon-based negative electrode material or not can obviously improve the energy density of the lithium battery once the silicon-based negative electrode material is successfully applied, so that the one-time charging endurance of 1000 kilometers becomes possible.
In order to solve the problems, scientific researchers adopt methods such as carbon coating, buffer space reservation and the like to improve the comprehensive electrical property of the silicon-based material. Chinese patent application publication No. CN102496701A reports a coated silicon-carbon negative electrode material for lithium ion batteries, in which silicon powder particles are coated with carbon nanotubes and amorphous carbon, so that the electrical conductivity and ionic conductivity of the material are improved, and the cycle performance is significantly improved. The chinese patent application with publication number CN103490045A reports that a composite system of silicon particles prepared by a CVD method and wrapped by an amorphous carbon layer improves the structure and conductivity of the silicon material, and can inhibit the volume effect during the insertion and extraction of lithium to a certain extent, thereby improving the cycle performance of the material. However, the CVD method is difficult to control and has many uncertainties, so that it is difficult to realize mass production. Chinese patent application CN102332571A discloses a silicon-carbon composite negative active material and a manufacturing method thereof, in the disclosure, a carbon layer is deposited on the surface of silicon in advance, and then mixed with an organic polymer, and carbonized after spray granulation to obtain a composite structure with silicon implanted in the core. However, in the structure, firstly, the surface of silicon needs to be etched, and then carbon is deposited, so that the process is complex; and the spraying process is complicated and the equipment is expensive.
Therefore, the method solves the dispersibility of the nano silicon particles in the silicon-carbon negative electrode material, reduces the agglomeration of the nano silicon particles, effectively inhibits the volume effect of silicon, improves the cycle performance and specific capacity of the silicon-carbon composite negative electrode material, and is one of the difficult problems to be solved in the field of preparing high-capacity silicon-based negative electrode materials.
Disclosure of Invention
The invention aims to solve the problems of serious agglomeration and serious volume expansion of a silicon-based negative electrode material in the prior art, and provides a silicon-carbon negative electrode material, a preparation method and application thereof and a lithium ion battery. The silicon-carbon cathode material provided by the invention can improve the dispersibility of nano silicon, relieve the volume expansion of silicon, improve the cycling stability of the material, and can improve the energy density of a lithium battery when being applied to the lithium battery.
In order to achieve the above object, a first aspect of the present invention provides a silicon-carbon negative electrode material, which includes a carbonaceous material, and a silicon-containing material layer and an amorphous carbon layer sequentially coated on an outer surface of the carbonaceous material.
Preferably, the silicon-containing material layer also contains phosphorus, and further preferably, in the silicon-carbon negative electrode material, the mass ratio of the phosphorus to the silicon-containing material is 0.01-0.28: 1.
the second aspect of the invention provides a preparation method of a silicon-carbon negative electrode material, which comprises the following steps:
(1) mixing a carbon-containing substance with a chain polymer solution, then adding a silicon source into the mixture, and separating the obtained mixture to obtain a solid substance;
(2) and blending the solid substance and a carbon source precursor, and then roasting.
The third aspect of the invention provides the silicon-carbon negative electrode material prepared by the preparation method.
The fourth aspect of the invention provides an application of the silicon-carbon negative electrode material in a lithium ion battery.
The invention provides a lithium ion battery, which comprises the silicon-carbon negative electrode material, a positive electrode material containing lithium element, a diaphragm and electrolyte.
The silicon-carbon cathode material provided by the invention has a carbon-silicon-carbon structure, and the inner layer carbon core (carbon-containing substance) provides a buffer space to relieve the volume expansion of silicon in the charge and discharge processes. The silicon-containing material layer plays a role in improving the capacity in the whole system, and the amorphous carbon layer can coat all the silicon-containing materials, so that the side reaction of the active material and the electrolyte is avoided, and the volume effect of silicon in a high lithium removal state can be inhibited. Preferably, phosphorus is introduced into the silicon-containing material layer, so that the possibility of agglomeration of silicon in the preparation and charge-discharge processes can be remarkably reduced, and the electrical property deterioration caused by agglomeration of silicon powder is improved.
The silicon-carbon negative electrode material provided by the invention greatly improves the reversible capacity and the cycling stability of the negative electrode material in the using process, and can obviously improve the energy density of a lithium battery. As can be seen from example 1, the silicon carbon negative electrode material provided by the invention (reversible capacity 517mAh g)-1) Under the constant current discharge rate of 0.5C, after 600 cycles, the capacity retention rate can reach more than 80%.
Drawings
Fig. 1 is an SEM photograph of the flake graphite used in example 1;
FIG. 2 is an SEM photograph of a silicon-containing material coated in example 1;
FIG. 3 is an SEM photograph of the silicon carbon anode material obtained in example 1;
FIG. 4 is a cycle stability test curve of the silicon carbon anode material obtained in example 1;
FIG. 5 is a cycle stability test curve of the negative electrode material for a lithium battery in comparative example 1;
FIG. 6 is a cycle stability test curve of a negative electrode material for a lithium battery in example 11;
fig. 7 is a cycle stability test curve of the negative electrode material for the lithium battery in comparative example 2.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the median diameter refers to a diameter corresponding to a cumulative particle size distribution percentage of 50%, and is usually used to represent an average particle size of the powder. In the present invention, the median particle diameter of the silicon-carbon negative electrode material can be obtained by dynamic light scattering characterization without specific indication.
The invention provides a silicon-carbon negative electrode material, which comprises a carbon-containing substance, a silicon-containing material layer and an amorphous carbon layer, wherein the silicon-containing material layer and the amorphous carbon layer are sequentially coated on the outer surface of the carbon-containing substance.
In the present invention, the sequential coating means that the outer surface of the carbonaceous material is coated with a silicon-containing material layer, and the outer surface of the silicon-containing material layer is coated with an amorphous carbon layer. The coating of the invention refers to an assembly structure formed by uniformly coating one material with another material through chemical bonds or other acting forces.
According to the invention, specifically, the silicon-containing material layer contains a silicon-containing material. The present invention provides a wide range of options for the form in which the silicon-containing material may be present, for example as particles and/or as a film.
According to the present invention, preferably, the silicon-containing material is selected from at least one of elemental silicon, SiOx and silicon-containing alloys, wherein 0.6< x < 1.5. The adoption of the preferred embodiment is more beneficial to further improving the reversible capacity of the silicon-carbon negative electrode material. The silicon-containing material can be obtained commercially or prepared by the existing method.
Preferably, the silicon-containing alloy is selected from at least one of a silicon-aluminum alloy, a silicon-magnesium alloy, a silicon-zirconium alloy, and a silicon-boron alloy. The invention has a wide selection range of the content of silicon in the silicon-containing alloy, for example, the content of silicon is 10-50 wt% based on the total amount of the silicon-containing alloy. The present invention is not particularly limited to the method for producing the silicon-containing alloy, and a specific method for producing the silicon-containing alloy is provided. The preparation method of the silicon-containing alloy preferably comprises the following steps: 1) carrying out ball milling on aluminum powder and silicon powder for 30min under the protection of inert atmosphere; 2) the mixture is treated at 900 ℃ for 10 h.
According to the present invention, preferably, the silicon-containing material is elemental silicon and/or a silicon-aluminum alloy.
Preferably, the siliceous material has a median particle size of 0.1 to 5 μm, and even more preferably, the siliceous material has a median particle size of 0.1 to 0.5 μm.
According to a preferred embodiment of the present invention, the silicon-containing material layer further contains phosphorus. The content of the phosphorus element is selected in a wide range, and can be properly selected according to the amount of the silicon-containing material, and preferably, in the silicon-carbon negative electrode material, the mass ratio of the phosphorus element to the silicon-containing material is 0.01-0.28: 1, more preferably 0.07 to 0.15: 1. by adopting the preferred embodiment, the modification of the silicon-containing material by the phosphorus element is facilitated, the possibility of agglomeration of silicon in the preparation and charge-discharge processes is remarkably reduced, and the electrical property deterioration caused by the agglomeration of silicon powder is further improved.
According to a preferred embodiment of the present invention, the mass ratio of the carbonaceous substance, the amorphous carbon layer, and the silicon-containing material is 1 to 20: 0.8-2: 1, more preferably 2 to 10: 1-1.3: 1. by adopting the preferred embodiment, the reversible capacity and the cycling stability of the negative electrode material can be improved, and the energy density of the lithium battery can be further improved.
According to the present invention, it is preferable that the silicon carbon anode material has a median particle diameter of 1 to 50 μm, for example, 1 μm, 5 μm, 10 μm, 15 μm, 25 μm, 50 μm, and any value in a range of any two of these values. Still more preferably, the silicon carbon anode material has a median particle diameter of 5 to 25 μm.
According to the present invention, preferably, the carbonaceous material is selected from at least one of natural graphite, artificial graphite, and needle coke. The carbonaceous material may be obtained commercially or may be prepared by itself, and the present invention is not particularly limited thereto. The natural graphite in the present invention is not particularly limited, and may be, for example, flake graphite.
Preferably, the carbonaceous material is flake graphite and/or needle coke.
The amorphous carbon layer is not particularly limited in the present invention, and for example, the amorphous carbon layer can be obtained by firing a carbon source precursor. Preferably, the carbon source precursor is selected from at least one of pitch, polyacrylonitrile, phenolic resin, epoxy resin, polyfurfuryl alcohol, glucose and cellulose, and is preferably selected from at least one of pitch, polyacrylonitrile and phenolic resin. By adopting the preferred embodiment, the complete coating of the amorphous carbon layer is facilitated, and the electrochemical performance of the prepared cathode material is further improved.
The asphalt of the present invention includes petroleum asphalt, coal tar asphalt, natural asphalt and modified asphalt, and has a meaning conventionally understood by those skilled in the art, and is commercially available.
The second aspect of the invention provides a preparation method of a silicon-carbon negative electrode material, which comprises the following steps:
(1) mixing a carbon-containing substance with a chain polymer solution, then adding a silicon source into the mixture, and separating the obtained mixture to obtain a solid substance;
(2) and blending the solid substance and a carbon source precursor, and then roasting.
According to the preparation method provided by the invention, the selection of the carbon-containing substance is as described above, and the details are not repeated.
According to the present invention, the silicon source may be the above-mentioned silicon-containing material, or may be a silicon-containing substance that can be converted into the above-mentioned silicon-containing material by the calcination in step (2), and preferably, the silicon source is the above-mentioned silicon-containing material, and the specific kind and the medium particle size thereof are selected as described above, and the details of the present invention are not repeated herein.
According to the present invention, it is preferable that the chain polymer contains at least one of a hydroxyl group, an ester group, and an amide group. For example, the chain polymer is preferably a substance containing a repeating unit of a carboxyl group, a hydroxyl group, an ester group or an amide group.
Preferably, the chain polymer is at least one selected from the group consisting of polyacrylic acid, polyacrylate, sodium alginate, polyurethane, and sodium carboxymethyl cellulose, and more preferably polyacrylic acid. By adopting the preferred embodiment, carboxyl in the polyacrylic acid can form hydrogen bonds with hydroxyl on the surface of the silicon-containing material, and the coating of the silicon-containing material is facilitated.
In the present invention, the molecular weight of the chain polymer is selected from a wide range, and the weight average molecular weight of the chain polymer is preferably 2000-5000000, more preferably 80000-300000.
According to the present invention, the chain polymer is preferably used in an amount of 0.1 to 1 part by weight, more preferably 0.1 to 0.5 part by weight, relative to 1 part by weight of the carbonaceous material.
The concentration of the chain polymer solution in the present invention is selected from a wide range, preferably from 3 to 20% by weight, more preferably from 3 to 8% by weight.
In the present invention, the solvent in the chain polymer solution is selected from a wide range as long as the solvent can form a solution with the chain polymer, and preferably, the solvent in the chain polymer solution is at least one of water, ethanol, acetone, N' N-dimethylformamide and N-methylpyrrolidone.
The specific embodiment of mixing the carbon-containing substance and the chain polymer solution in step (1) is not particularly limited, the mixing is preferably performed under stirring conditions, the stirring time and the stirring speed are not particularly limited, so as to enable the solid to be uniformly dispersed, the specific operation is well known to those skilled in the art, and the detailed description is omitted here.
In the present invention, the silicon source may be directly introduced in step (1), or the silicon source may be introduced in the form of a solution, and preferably, the silicon source is introduced in the form of a solution.
According to the method provided by the invention, preferably, the solution also contains a phosphorus source. Namely, a silicon source and a phosphorus source are mixed in the presence of a solvent to obtain a solution, and then the solution is introduced. By adopting the preferred embodiment, the modification of the silicon source by the phosphorus element is facilitated, the possibility of agglomeration of silicon in the preparation and charging and discharging processes is remarkably reduced, and the electrical property deterioration caused by the agglomeration of silicon powder is further improved.
According to the invention, preferably, the source of phosphorus is a polyphosphoric acid, preferably phytic acid; among them, the phytic acid is a commonly understood meaning of those skilled in the art, and is commercially available.
According to the invention, the mass ratio of the phosphorus source to the silicon source, calculated as phosphorus element, is preferably between 0.01 and 0.28: 1, preferably 0.07-0.15: 1.
according to a preferred embodiment of the present invention, the step (1) comprises:
(1-1) mixing a silicon source and a phosphorus source in the presence of a solvent to obtain a solution A;
(1-2) mixing a carbonaceous material with a solution of a chain polymer, then adding the solution A thereto, and separating the resulting mixture to obtain a solid material.
According to an embodiment of the present invention, the solvent in step (1-1) is preferably at least one of water, ethanol, acetone, N' N-dimethylformamide, and N-methylpyrrolidone.
According to an embodiment of the present invention, the step (1-1) includes: the phosphorus source is mixed with a solvent to obtain a phosphorus source solution (the concentration may be 10-45 wt%), and then a silicon source is added for the mixing. The mixing conditions in the present invention are not particularly limited, and the mixing may be carried out under stirring for a period of time of 1 to 8 hours, for example.
According to one embodiment of the present invention, in step (1-2), after the addition of the solution A, stirring is continued (preferably for 1-6 hours), and then the separation is performed.
The separation is not particularly limited in the present invention as long as the solid and the liquid are separated, and filtration, for example, suction filtration, is preferable.
According to the method provided by the present invention, the selection of the carbon source precursor can be as described above, and is not described herein again.
According to the invention, preferably, the mass ratio of the carbon-containing substance, the carbon source precursor calculated by carbon element and the silicon source is 1-20: 0.8-2: 1, more preferably 2 to 10: 1-1.3: 1. by adopting the preferred embodiment, the reversible capacity and the cycling stability of the negative electrode material can be improved, and the energy density of the lithium battery can be further improved.
The amount of carbon source precursor added can be selected by those skilled in the art according to the above ratio by the amount of carbon in the carbon source precursor. In the embodiment of the invention, a carbon source precursor is taken as an example for illustration, the residual carbon content of the pitch is 0.2-0.8 wt%, and on the basis, the mass ratio of the carbon source precursor to the silicon source is 1-10: 1, more preferably 1.25 to 6.5: 1.
according to the present invention, preferably, the blending of step (2) comprises at least one of ball milling, spray drying and shear dispersion. By adopting the preferred embodiment, the carbon source precursor is more beneficial to uniformly coating the silicon surface.
The specific operations of ball milling, spray drying and shear dispersion are not particularly limited in the present invention, and may be selected according to the median particle size of the target product. Preferably, the specific conditions of ball milling, spray drying and shear dispersion are such that the median particle size of the prepared silicon carbon anode material is 1-50 μm, more preferably 5-25 μm.
According to the present invention, the solvent used for ball milling, spray drying, and shear dispersion of the solid may be a solvent conventionally used in the art, and is preferably at least one of ethanol, acetone, tetrahydrofuran, N-dimethylformamide, and N-methylpyrrolidone.
The amount of solvent added in the present invention is selected within a wide range, for example, the slurry obtained by mixing has a solid content of 10 to 35% by weight.
According to a specific embodiment of the present invention, the method further comprises separating the mixed materials after the mixing in the step (2), and subjecting the separated solids to the roasting. The separation may be a separation method conventional in the art, such as centrifugation, filtration separation. Preferably, the method further comprises drying the solid and then performing the roasting. The invention has wide selection range of drying conditions, and preferably, the temperature is 80-150 ℃ and the time is 1-10 h.
According to the present invention, preferably, the conditions of the firing include: under the inert atmosphere, the temperature is 600-1000 ℃, and preferably 700-900 ℃; the time is 10-240min, preferably 20-60 min. The inert atmosphere may be provided by at least one of nitrogen, helium, argon, and krypton, and the embodiment of the present invention is partially exemplified by nitrogen, but the present invention is not limited thereto.
In the present invention, the heating rate of the calcination is not particularly limited, and may be, for example, 1 to 10 ℃/min. In the embodiment of the present invention, the example is given by taking 5 ℃/min as an example, and the present invention is not limited thereto.
The third aspect of the invention provides the silicon-carbon negative electrode material prepared by the preparation method. The structure and composition characteristics of the silicon-carbon negative electrode material are as described above, and are not described in detail herein.
The fourth aspect of the invention provides an application of the silicon-carbon negative electrode material in a lithium ion battery. In the research process, the inventor of the invention finds that the energy density of a lithium battery can be improved by using the silicon-carbon negative electrode material provided by the invention in the lithium battery.
The invention provides a lithium ion battery, which comprises the silicon-carbon negative electrode material, a positive electrode material containing lithium element, a diaphragm and electrolyte.
The structure of the lithium ion battery provided by the invention can be known to those skilled in the art, and generally, the separator is positioned between the positive plate and the negative plate. The anode piece contains the anode material, and the cathode piece contains the silicon-carbon cathode material. In the present invention, the specific composition of the lithium element-containing positive electrode material is not particularly limited, and may be a lithium element-containing positive electrode material conventionally used in the art.
According to the lithium ion battery provided by the invention, the separator can be selected from various separators used in lithium ion batteries known to those skilled in the art, and can be, for example, a polypropylene microporous membrane, a polyethylene felt, a glass fiber felt or superfine glass fiber paper.
According to the lithium ion battery provided by the invention, the electrolyte can be various conventional electrolytes, such as a nonaqueous electrolyte. The nonaqueous electrolytic solution is a solution of an electrolytic lithium salt in a nonaqueous solvent, and a conventional nonaqueous electrolytic solution known to those skilled in the art can be used. For example, the electrolyte may be selected from lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium tetrafluoroborate (LiBF)4) Lithium hexafluoroarsenate (LiAsF)6) And lithium hexafluorosilicate (LiSiF)6) At least one of (1). The non-aqueous solvent may be selected from a mixed solution of a chain ester and a cyclic ester, wherein the chain ester may be at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), propyl methyl carbonate (MPC), and dipropyl carbonate (DPC). The cyclic acid ester may be at least one of Ethylene Carbonate (EC), Propylene Carbonate (PC), and Vinylene Carbonate (VC).
The present invention will be described in detail below by way of examples. In the following examples and comparative examples, the morphology of the silicon carbon negative electrode material was characterized by using a scanning electron microscope, specifically, the scanning electron microscope is TECNALG2F20(200kv) from FEI company, usa, and the test conditions are as follows: the sample was pressed directly onto the sample stage containing the conductive tape and then observed by insertion into an electron microscope. The observation was performed using 8000 magnifications. The content of each component is obtained by measuring the loss amount of the carbon source precursor under the roasting condition and calculating the feeding ratio.
In the following examples and comparative examples, electrochemical performance of assembled lithium ion batteries was tested using the wuhan blue battery test system (CT 2001B). The test conditions included: the voltage range is 0.005V-3V, and the current range is 0.05A-2A. Each sample was assembled with 10 coin cells and the cell performance was tested at the same voltage and current and averaged.
In the following examples and comparative examples, the coal tar pitch was obtained from Longxin Dow Co., Ltd under the trade designation of low temperature pitch (100-.
In the following examples and comparative examples, the room temperature is 25 ℃.
Among them, polyacrylic acid, polyacrylate, sodium carboxymethylcellulose and sodium alginate are commercially available from alatin reagent.
Example 1
(1) Slowly adding 1g of 50 wt% phytic acid aqueous solution into 20ml of ethanol, stirring uniformly, and adding D501g of 150nm silicon powder, and stirring for 4 hours.
(2) Taking 50g (mass fraction of 4 wt%) of an ethanol solution of polyacrylic acid with the weight-average molecular weight of 240000, adding 10g of crystalline flake graphite (shown in figure 1), stirring at room temperature until the solid is uniformly dispersed, then adding the solution in the step (1), continuing stirring for 1h after the addition is finished, and carrying out vacuum filtration.
(3) And (2) putting the suction-filtered dry solid (shown in figure 2) into a 200ml ball milling tank, adding 2g of medium-temperature pitch, carrying out ball milling for 30min, putting the obtained solid into a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 30min under the nitrogen atmosphere, and naturally cooling to room temperature after finishing, thus obtaining the silicon-carbon negative electrode material S-1. The composition of the silicon carbon anode material S-1 is listed in table 1.
Fig. 1 is an SEM photograph of the flake graphite, and fig. 2 is an SEM photograph of carbon-silicon particles coated with a silicon-containing material layer. As can be seen from comparison between fig. 1 and fig. 2, the surface of the carbonaceous material is uniformly coated with the silicon nanoparticles through step (2). Fig. 3 is an SEM photograph of the obtained silicon-carbon negative electrode material, and it can be seen from comparison of fig. 2 that the surface of the particles coated with the silicon-containing material layer has been uniformly coated with the pitch pyrolytic carbon, and the coated material has a good sphericity and a median particle size of about 22 μm.
The silicon-carbon negative electrode material S-1 obtained in example 1 and a metal lithium sheet were used as a positive electrode and a negative electrode, respectively, and 1mol/L LiPF was used6The solution (ethylene carbonate and diethyl carbonate are mixed in a volume ratio of 3: 7 as a solvent) is used as an electrolyte, a polypropylene microporous membrane is used as a diaphragm, and the diaphragm is assembled into a CR2016 button cell, so that the cycling stability of the lithium-containing silicon-carbon negative electrode material S-1 in the embodiment is characterized.
Fig. 4 is a cycle stability test curve (discharge current 0.5C) for a coin cell based on the lithium-containing silicon-carbon negative electrode material S-1 described in example 1. As can be seen from FIG. 4, the silicon-carbon negative electrode material S-1 in example 1 has a capacity retention rate of more than 80% after 550 cycles at a constant current discharge rate of 0.5C.
Comparative example 1
(1) Slowly adding 1g of 50 wt% phytic acid aqueous solution into 20ml of ethanol, stirring uniformly, and adding D50Stirring for 4h for 1g of 150nm silicon powder, and vacuum filtering.
(2) And (3) putting the suction-filtered dry solid into a ball milling tank of 200ml, adding 2g of medium-temperature pitch, carrying out ball milling for 30min, putting the obtained solid into a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 30min under the nitrogen atmosphere, and naturally cooling to room temperature to obtain the silicon-carbon negative electrode material D-1.
A battery was assembled and tested for electrical properties according to the method of example 1, except that S-1 was replaced with the material D-1 prepared in comparative example 1. Fig. 5 is a cycle stability test curve for coin cells based on the material described in comparative example 1. As shown in the figure, the capacity retention rate of the material of comparative example 1 is only 60% after 100 cycles at a constant current discharge rate of 0.5C.
Comparative example 2
(1) Slowly adding 50 wt% phytic acid water solution 1gAdding into 20ml ethanol, stirring, adding D501g of 150nm silicon powder, and stirring for 4 hours.
(2) Taking 50g (mass fraction of 4 wt%) of an ethanol solution of polyacrylic acid with the weight-average molecular weight of 240000, adding 10g of crystalline flake graphite, stirring at room temperature until the solid is uniformly dispersed, then adding the solution obtained in the step (1), continuing stirring for 1h after the addition is finished, and carrying out vacuum filtration.
(3) And (3) placing the suction-filtered dry solid in a tubular furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 30 minutes in a nitrogen atmosphere, and naturally cooling to room temperature after the temperature is up to obtain the silicon-carbon negative electrode material D-2.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon carbon negative electrode material S-1 was replaced with the material prepared in comparative example 2. Fig. 7 is a cycle stability test curve for coin cells based on the material described in comparative example 2. The results show that the capacity retention rate of the material of comparative example 2 is about 40% after 100 cycles at a constant current discharge rate of 0.5C.
Example 2
(1) Slowly adding 50 wt% phytic acid water solution 0.5g into 20ml ethanol, stirring well, adding D501g of 150nm silicon powder, and stirring for 4 hours.
(2) Taking 50g (mass fraction of 4 wt%) of an ethanol solution of polyacrylic acid with the weight-average molecular weight of 240000, adding 10g of needle coke, stirring at room temperature until the solid is uniformly dispersed, then adding the solution obtained in the step (1), continuing stirring for 1h after the addition is finished, and carrying out vacuum filtration.
(3) And (3) putting the suction-filtered dry solid into a ball milling tank of 200ml, adding 4g of medium-temperature pitch, carrying out ball milling for 30min, putting the obtained solid into a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 30min under the nitrogen atmosphere, and naturally cooling to room temperature to obtain the silicon-carbon negative electrode material S-2. The composition of the silicon carbon anode material S-2 is listed in table 1.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon carbon negative electrode material S-1 was replaced with the material prepared in example 2. The test result shows that the capacity retention rate of the material in example 2 is about 85% after 500 cycles under the constant current discharge rate of 0.5C.
Example 3
(1) Slowly adding 0.08g of 50 wt% phytic acid aqueous solution into 20ml of ethanol, stirring uniformly, and adding D501g of 150nm silicon powder, and stirring for 4 hours.
(2) Taking 50g (mass fraction of 4 weight percent) of ethanol solution of polyacrylic acid with the weight-average molecular weight of 240000, adding 10g of artificial graphite (trade mark S-216), stirring at room temperature until the solid is uniformly dispersed, then adding the solution in the step (1), continuing stirring for 1h after the addition is finished, and carrying out vacuum filtration.
(3) And (3) putting the suction-filtered dry solid into a ball milling tank of 200ml, adding 1.6g of medium-temperature pitch, carrying out ball milling for 30min, putting the obtained solid into a tubular furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 30min under the nitrogen atmosphere, and naturally cooling to room temperature to obtain the silicon-carbon negative electrode material S-3. The composition of the silicon carbon anode material S-3 is listed in table 1.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon carbon negative electrode material S-1 was replaced with the material prepared in example 3. The test result shows that the capacity retention rate of the material in example 3 is about 82% after 600 cycles under the constant current discharge rate of 0.5C.
Example 4
(1) Slowly adding 2g of 50 wt% phytic acid aqueous solution into 20ml of ethanol, stirring uniformly, and adding D501g of 150nm silicon powder, and stirring for 4 hours.
(2) And (2) taking 50g of sodium alginate aqueous solution with the weight-average molecular weight of 130000 (mass fraction of 4 wt%), adding 10g of crystalline flake graphite, stirring at room temperature until the solid is uniformly dispersed, then adding the solution in the step (1), continuing stirring for 1h after the addition is finished, and carrying out vacuum filtration.
(3) And (3) putting the suction-filtered dry solid into a stirring tank of 200ml, adding 2.6g of medium-temperature pitch, stirring at the rotating speed of 2000r/min for 5min, putting the obtained solid into a tubular furnace, heating to 850 ℃ at the speed of 5 ℃/min, preserving the heat for 30min under the nitrogen atmosphere, and naturally cooling to room temperature to obtain the silicon-carbon negative electrode material S-4. The composition of the silicon carbon anode material S-4 is listed in table 1.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon carbon negative electrode material S-1 was replaced with the material prepared in example 4. The test result shows that the capacity retention rate of the material in example 4 is about 85% after 400 cycles under the constant current discharge rate of 0.5C.
Example 5
(1) Slowly adding 0.8g of 50 wt% phytic acid aqueous solution into 20ml of ethanol, stirring uniformly, and adding D501g of 150nm silicon powder, and stirring for 4 hours.
(2) And (2) taking 50g (mass fraction of 4 wt%) of sodium carboxymethylcellulose aqueous solution with the weight-average molecular weight of 850000, adding 10g of crystalline flake graphite, stirring at room temperature until the solid is uniformly dispersed, then adding the solution obtained in the step (1), continuing stirring for 1h after the addition is finished, and performing vacuum filtration.
(3) And (3) putting the suction-filtered dry solid into a ball milling tank of 200ml, adding 3g of medium-temperature pitch, carrying out ball milling for 30min, putting the obtained solid into a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 30min under the nitrogen atmosphere, and naturally cooling to room temperature to obtain the silicon-carbon negative electrode material S-5. The composition of the silicon carbon anode material S-5 is listed in table 1.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the lithium-containing silicon carbon negative electrode material S-1 was replaced with the material prepared in example 5. The test result shows that the capacity retention rate of the material in example 5 is about 80% after 500 cycles under the constant current discharge rate of 0.5C.
Example 6
(1) Slowly adding 1g of 50 wt% phytic acid aqueous solution into 20ml of ethanol, stirring uniformly, and adding D501g of 150nm silicon powder, and stirring for 4 hours.
(2) And (2) taking 50g (mass fraction is 7 weight percent) of polyacrylic acid ethanol solution with the weight-average molecular weight of 240000, adding 20g of crystalline flake graphite, stirring at room temperature until the solid is uniformly dispersed, then adding the solution in the step (1), continuously stirring for 1h after the addition is finished, and carrying out vacuum filtration.
(3) And (3) putting the suction-filtered dry solid into a ball milling tank of 200ml, adding 5g of low-temperature asphalt, carrying out ball milling for 100min, putting the obtained solid into a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 30min under the nitrogen atmosphere, and naturally cooling to room temperature to obtain the silicon-carbon negative electrode material S-6. The composition of the silicon carbon anode material S-6 is listed in table 1.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon carbon negative electrode material S-1 was replaced with the material prepared in example 6. The test result shows that the capacity retention rate of the material in example 6 is about 83% after 600 cycles under the constant current discharge rate of 0.5C.
Example 7
(1) Slowly adding 2.5g of 20 weight percent phytic acid aqueous solution into 20ml of ethanol, stirring uniformly, and adding D501g of 150nm silicon powder, and stirring for 4 hours.
(2) And (2) taking 50g (mass fraction of 15 wt%) of a polyacrylic acid ethanol solution with the weight-average molecular weight of 240000, adding 15g of crystalline flake graphite, stirring at room temperature until the solid is uniformly dispersed, then adding the solution obtained in the step (1), continuously stirring for 1h after the addition is finished, and carrying out vacuum filtration.
(3) And (3) putting the suction-filtered dry solid into a ball milling tank of 200ml, adding 5g of low-temperature asphalt, carrying out ball milling for 100min, putting the obtained solid into a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 30min under the nitrogen atmosphere, and naturally cooling to room temperature to obtain the silicon-carbon negative electrode material S-7. The composition of the silicon carbon anode material S-7 is listed in table 1.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon carbon negative electrode material S-1 was replaced with the material prepared in example 7. The test result shows that the capacity retention rate of the material described in example 7 is about 80% after 300 cycles under the constant current discharge rate of 0.5C.
Example 8
(1) Slowly adding 1g of 50 wt% phytic acid aqueous solution into 20ml of ethanol, stirring uniformly, and adding D501g of 150nm silicon powder, and stirring for 4 hours.
(2) Taking 50g of sodium alginate aqueous solution with the weight-average molecular weight of 130000 (mass fraction of 6 weight percent), adding 15g of crystalline flake graphite, stirring at room temperature until the solid is uniformly dispersed, then adding the solution in the step (1), continuing stirring for 1h after the addition is finished, and carrying out vacuum filtration.
(3) And (3) putting the suction-filtered dry solid into a ball milling tank of 200ml, adding 3g of low-temperature asphalt, carrying out ball milling for 100min, putting the obtained solid into a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 30min under the nitrogen atmosphere, and naturally cooling to room temperature to obtain the silicon-carbon negative electrode material S-8. The composition of the silicon carbon anode material S-8 is listed in table 1.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon carbon negative electrode material S-1 was replaced with the material prepared in example 8. The test result shows that the capacity retention rate of the material of example 8 is about 80% after 500 cycles under the constant current discharge rate of 0.5C.
Example 9
(1) Slowly adding 1g of 50 wt% phytic acid aqueous solution into 20ml of ethanol, stirring uniformly, and adding D50The solution was stirred for 4 hours for 1g of 150nm silicon oxide (SiOx, x ═ 1.2).
(2) Taking 50g (mass fraction of 4 weight percent) of polyacrylic acid ethanol solution with the weight-average molecular weight of 240000, adding 10g of artificial graphite (trade mark S-216), stirring at room temperature until the solid is uniformly dispersed, then adding the solution in the step (1), continuing stirring for 1h after the addition is finished, and carrying out vacuum filtration.
(3) And (3) putting the suction-filtered dry solid into a ball milling tank of 200ml, adding 2g of medium-temperature pitch, carrying out ball milling for 30min, putting the obtained solid into a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 30min under the nitrogen atmosphere, and naturally cooling to room temperature to obtain the silicon-carbon negative electrode material S-9. The composition of the silicon carbon anode material S-9 is listed in table 1.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon carbon negative electrode material S-1 was replaced with the material prepared in example 9. The test result shows that the capacity retention rate of the material of example 9 is about 85% after 600 cycles under the constant current discharge rate of 0.5C.
Example 10
(1) Slowly adding 1g of 50 wt% phytic acid aqueous solution into 20ml of ethanol, stirring uniformly, and adding D501g of 200nm Si-Al alloy (Si content about 20 wt.%), and stirring for 4 hr.
(2) Taking 50g (mass fraction of 4 weight percent) of polyacrylic acid ethanol solution with the weight-average molecular weight of 240000, adding 10g of artificial graphite (trade mark S-216), stirring at room temperature until the solid is uniformly dispersed, then adding the solution in the step (1), continuing stirring for 1h after the addition is finished, and carrying out vacuum filtration.
(3) And (3) putting the suction-filtered dry solid into a ball milling tank of 200ml, adding 2g of medium-temperature pitch, carrying out ball milling for 30min, putting the obtained solid into a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 30min under the nitrogen atmosphere, and naturally cooling to room temperature to obtain the silicon-carbon negative electrode material S-10. The composition of the silicon carbon anode material S-10 is listed in table 1.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon carbon negative electrode material S-1 was replaced with the material prepared in example 10. The test result shows that the capacity retention rate of the material described in example 10 is about 85% after 500 cycles under the constant current discharge rate of 0.5C.
Example 11
(1) Get D501g of 150nm silica powder was slowly added to 20ml of ethanol and stirred for 4 hours.
(2) And (2) taking 50g (mass fraction of 4 wt%) of a polyacrylic acid ethanol solution with the weight-average molecular weight of 240000, adding 10g of crystalline flake graphite, stirring at room temperature until the solid is uniformly dispersed, then adding the solution obtained in the step (1), continuously stirring for 1h after the addition is finished, and carrying out vacuum filtration.
(3) And (3) putting the suction-filtered dry solid into a ball milling tank of 200ml, adding 2g of medium-temperature pitch, carrying out ball milling for 30min, putting the obtained solid into a tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 30min under the nitrogen atmosphere, and naturally cooling to room temperature to obtain the silicon-carbon negative electrode material S-11.
A battery was assembled and tested for electrical properties according to the method of example 1, except that the silicon carbon negative electrode material S-1 was replaced with the material prepared in example 11. Fig. 6 shows the cycle stability test curve of a coin cell based on the material described in example 11. The results show that the material of example 11 has a capacity retention of about 70% after 100 cycles at a constant current discharge rate of 0.5C.
TABLE 1
Figure BDA0002529057170000191
Note: the median particle size is the median particle size of the silicon-carbon negative electrode material.
The embodiment and the result show that the silicon-carbon negative electrode material provided by the invention can obviously improve the cycle stability of the silicon-carbon negative electrode material, and can improve the energy density of a lithium battery when being applied to the lithium battery.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (15)

1. The silicon-carbon negative electrode material is characterized by comprising a carbon-containing substance, a silicon-containing material layer and an amorphous carbon layer, wherein the silicon-containing material layer and the amorphous carbon layer are sequentially coated on the outer surface of the carbon-containing substance.
2. The silicon-carbon anode material of claim 1, wherein the silicon-containing material is selected from at least one of elemental silicon, SiOx, and silicon-containing alloys, where 0.6< x < 1.5;
preferably, the silicon-containing alloy is selected from at least one of a silicon-aluminum alloy, a silicon-magnesium alloy, a silicon-zirconium alloy, and a silicon-boron alloy;
preferably, the silicon-containing material is elemental silicon and/or a silicon-aluminum alloy;
preferably, the siliceous material has a median particle size of 0.1 to 5 μm;
preferably, the silicon-containing material layer also contains phosphorus;
preferably, in the silicon-carbon negative electrode material, the mass ratio of the phosphorus element to the silicon-containing material is 0.01-0.28: 1, preferably 0.07-0.15: 1.
3. the silicon-carbon anode material of claim 1 or 2, wherein the mass ratio of the carbonaceous substance, the amorphous carbon layer and the silicon-containing material is 1-20: 0.8-2: 1, more preferably 10 to 15: 1-1.3: 1.
4. silicon-carbon anode material according to any of claims 1 to 3, wherein the silicon-carbon anode material has a median particle size of 1 to 50 μm, more preferably 5 to 25 μm.
5. The silicon-carbon anode material according to any one of claims 1 to 4, wherein the carbonaceous matter is selected from at least one of natural graphite, artificial graphite, and needle coke; preferably, the natural graphite is flake graphite;
preferably, the carbonaceous material is flake graphite and/or needle coke.
6. The silicon-carbon anode material of any one of claims 1 to 5, wherein the amorphous carbon layer is obtained by roasting a carbon source precursor;
the carbon source precursor is selected from at least one of pitch, polyacrylonitrile, phenolic resin, epoxy resin, polyfurfuryl alcohol, glucose and cellulose, and is preferably selected from at least one of pitch, polyacrylonitrile and phenolic resin.
7. A preparation method of a silicon-carbon negative electrode material comprises the following steps:
(1) mixing a carbon-containing substance with a chain polymer solution, then adding a silicon source into the mixture, and separating the obtained mixture to obtain a solid substance;
(2) and blending the solid substance and a carbon source precursor, and then roasting.
8. The production method according to claim 7, wherein the carbonaceous matter is selected from at least one of natural graphite, artificial graphite, and needle coke; preferably, the natural graphite is flake graphite; further preferably, the carbonaceous material is flake graphite and/or needle coke;
preferably, the chain polymer contains at least one of a hydroxyl group, an ester group, and an amide;
preferably, the chain polymer is selected from at least one of polyacrylic acid, polyacrylate, sodium alginate, polyurethane and sodium carboxymethyl cellulose, and is more preferably polyacrylic acid;
preferably, the weight average molecular weight of the chain polymer is 2000-5000000, more preferably 80000-300000;
preferably, the chain polymer is used in an amount of 0.1 to 1 part by weight, more preferably 0.1 to 0.5 part by weight, relative to 1 part by weight of the carbonaceous material;
preferably, the concentration of the chain polymer solution is 3 to 20% by weight.
9. The method of claim 7, wherein the silicon source is selected from at least one of elemental silicon, SiOx, and silicon-containing alloys, wherein 0.6< x < 1.5;
preferably, the silicon-containing alloy is selected from at least one of a silicon-aluminum alloy, a silicon-magnesium alloy, a silicon-zirconium alloy, and a silicon-boron alloy;
preferably, the silicon source is elemental silicon and/or silicon-aluminum alloy;
preferably, the silicon source has a median particle size of 0.1 to 5 μm.
10. The method of claim 7, wherein the silicon source is introduced in the form of a solution, preferably the solution further comprises a phosphorous source;
preferably, the phosphorus source is a polyphosphoric acid, and further preferably phytic acid;
preferably, the mass ratio of the phosphorus source to the silicon source calculated by the phosphorus element is 0.01-0.28: 1, preferably 0.07-0.15: 1;
preferably, the step (1) comprises:
(1-1) mixing a silicon source and a phosphorus source in the presence of a solvent to obtain a solution A;
(1-2) mixing a carbonaceous material with a solution of a chain polymer, then adding the solution A thereto, and separating the resulting mixture to obtain a solid material.
11. The production method according to claim 7, wherein the carbon source precursor is selected from at least one of pitch, polyacrylonitrile, phenol resin, epoxy resin, polyfurfuryl alcohol, glucose, and cellulose, preferably at least one of pitch, polyacrylonitrile, and phenol resin;
preferably, the mass ratio of the carbon-containing substance, the carbon source precursor calculated by carbon element and the silicon source is 1-20: 0.8-2: 1, more preferably 10 to 15: 1-1.3: 1.
12. the method of any one of claims 7-11, wherein the blending of step (2) comprises at least one of solid ball milling, spray drying, and shear dispersion;
preferably, the roasting conditions in step (2) include: under the inert atmosphere, the temperature is 600-1000 ℃, and preferably 700-900 ℃; the time is 10-240min, preferably 20-60 min.
13. A silicon-carbon anode material produced by the production method according to any one of claims 7 to 12.
14. Use of the silicon carbon negative electrode material of any one of claims 1 to 6 and 13 in a lithium ion battery.
15. A lithium ion battery comprising the silicon-carbon negative electrode material according to any one of claims 1 to 6 and 13, a positive electrode material containing lithium element, a separator and an electrolyte;
preferably, the lithium ion battery is a liquid lithium ion battery, a semi-solid lithium ion battery or an all-solid lithium ion battery.
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