CN111525110B - Silicon-based composite anode material and preparation method and application thereof - Google Patents

Silicon-based composite anode material and preparation method and application thereof Download PDF

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CN111525110B
CN111525110B CN202010354160.1A CN202010354160A CN111525110B CN 111525110 B CN111525110 B CN 111525110B CN 202010354160 A CN202010354160 A CN 202010354160A CN 111525110 B CN111525110 B CN 111525110B
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silicon
coating layer
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carbon
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CN111525110A (en
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朱成奔
万远鑫
孔令涌
任望保
钟泽钦
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Shenzhen Dynanonic 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 preparation method of a silicon-based composite anode material, which comprises the following steps: (1) corroding the silicon monoxide particles to obtain silicon monoxide with a porous structure; (2) in the presence of a catalyst, growing carbon nanotubes on the surface and in the pores of the porous silicon oxide in situ; (3) performing carbon coating on the material obtained in the step (2) by adopting a chemical vapor deposition method to form a first coating layer; (4) and (4) preparing the material obtained in the step (3), graphite, a conductive agent, a binder and a solvent into mixed slurry, carrying out spray drying granulation on the mixed slurry, and forming a second coating layer outside the first coating layer. The preparation method has the advantages of simple process and low cost, and can be used for industrial production; meanwhile, the obtained silicon-based composite negative electrode material has good conductivity and cycling stability. The invention also provides a silicon-based composite anode material and application thereof.

Description

Silicon-based composite anode material and preparation method and application thereof
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a silicon-based composite negative electrode material and a preparation method and application thereof.
Background
Because the lithium ion battery has the advantages of high energy density, long cycle life, environmental friendliness and the like, the lithium ion battery is widely applied to the fields of portable electronic products such as mobile phones and notebook computers, new energy automobiles and energy storage, while the current commercialized lithium ion battery cathode material is a graphite carbon material, but the graphite carbon material has the problems of low theoretical capacity, poor compatibility with solvents, poor high-rate discharge performance and the like; therefore, the use of silicon-based materials with the advantages of high capacity, high safety, and wide raw material sources as negative active materials has become an important research direction for improving the energy density of lithium ion batteries.
However, the silicon-based negative electrode material generates larger volume expansion in the charging and discharging processes, so that the silicon-based negative electrode material can be pulverized and fall off in the charging and discharging processes, and electrochemical connection between active substances and between the active substances and a current collector is lost; meanwhile, the silicon-based negative electrode material cannot form a stable surface solid electrolyte film (namely SEI film) in the electrolyte, and a new SEI film is formed on the newly exposed silicon surface after the electrode structure is damaged, so that capacity attenuation and cycle reduction are further caused. In addition, the intrinsic conductivity of silicon is low, which restricts the migration rate of lithium ions, resulting in poor rate capability of the material.
Disclosure of Invention
In view of the above, the invention provides a silicon-based composite anode material for a lithium ion battery and a preparation method thereof. The preparation method of the silicon-based composite anode material is simple to operate and can be used for large-scale industrial production; the prepared silicon-based composite negative electrode material has good conductivity, extremely low volume expansion effect, large capacity, good cycle performance and other excellent electrochemical properties.
In a first aspect, the invention provides a preparation method of a silicon-based composite anode material, which comprises the following steps:
(1) corroding the silicon monoxide particles to obtain silicon monoxide with a porous structure;
(2) in the presence of a catalyst, growing carbon nanotubes on the surface and in the pores of the porous-structure silicon oxide in situ, wherein the mass ratio of the catalyst to the porous-structure silicon oxide is 1 (10-1000), and the aspect ratio of the carbon nanotubes is not less than 3000;
(3) performing carbon coating on the material obtained in the step (2) by adopting a chemical vapor deposition method to form a first coating layer;
(4) preparing the material obtained in the step (3) with graphite, a conductive agent, a binder and a solvent into mixed slurry, wherein the mass ratio of the material obtained in the step (3) to the graphite, the conductive agent and the binder is 100: (1-20): (0.5-5): 1-10);
spray drying and granulating the mixed slurry, and forming a second coating layer in which the graphite and the conductive agent are embedded outside the first coating layer to obtain the silicon-based composite negative electrode material; wherein a portion of the carbon nanotubes are interpenetrated from the second coating layer.
Wherein, the preparation method also comprises the step of removing the catalyst, which specifically comprises the following steps: after the carbon nanotubes are grown in situ in the step (2) or after the spray drying granulation in the step (4), acid washing is performed to remove the catalyst. The acid washing can remove the catalyst remained in the material, reduce the content of the magnetic substance in the obtained silicon-based composite negative electrode material, avoid the risk that the magnetic substance increases the self-discharge of the battery when the silicon-based composite negative electrode material is applied to the battery, further avoid the micro short circuit in the battery, and improve the safety performance and the service life of the battery.
Optionally, the pickling process comprises: adopting at least one of concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid, concentrated phosphoric acid, hydrofluoric acid, perchloric acid and dichromic acid as a pickling solution, putting the material obtained in the step (2) or the crude product obtained after spray drying and granulation in the step (4) into the pickling solution, and stirring for 0.5-10h at 20-80 ℃; and then carrying out solid-liquid separation, washing the obtained solid until the pH value of the cleaning solution is neutral, and drying.
Wherein, the solid-liquid separation can be filtration, centrifugation, standing and the like, and the drying can be hot air drying at 50-200 ℃.
Optionally, in the step (1), the particle diameter of D50 of the silica particles is 1-20 μm.
Optionally, in the step (1), the etching solution used for etching the silicon monoxide particles is an acidic etching solution or an alkaline etching solution. Wherein the acidic corrosive liquid is hydrofluoric acid; the alkaline corrosive liquid is one or more of sodium hydroxide and potassium hydroxide. Further, the mass concentration of the acidic corrosive liquid is 1-30%; preferably 5 to 30%. The mass concentration of the alkaline corrosive liquid is 1-30%, preferably 1-10%.
In one embodiment of the present invention, the etching is performed for 0.5 to 4 hours. If the corrosion time is too short, the pore-forming of the silicon oxide is insufficient, and if the corrosion time is too long, the reaction of the silicon oxide raw material is excessive, so that the Si content in the silicon-based composite anode material is too low, and the specific capacity of the battery is reduced when the silicon oxide raw material is applied to the battery; in addition, too long corrosion time can also result in too high porosity, which in turn leads to easier breakage and powdering of the silicon-based composite anode material, resulting in battery failure.
Optionally, the pore size of the porous structure silica is 10-300 nm. The porosity is 10-80%. The silicon oxide has a porous structure after being corroded, so that the surface area of the original material is increased, and more attachment points are provided for a catalyst for subsequent in-situ growth of the carbon nano tube; and provides a buffer effect for the volume expansion of the silicon monoxide in the charging and discharging processes. Preferably, the porosity of the silica having a porous structure is 20 to 50%.
In the invention, in the step (2), the mass ratio of the catalyst to the porous-structure-containing silica is 1 (10-1000). The mass ratio can ensure the uniform growth of the subsequent carbon nano tube on the porous silica, and the generated carbon nano tube can improve the conductivity of the silica without influencing the dispersibility of the whole material. Preferably, the mass ratio of the catalyst to the porous-structure-containing silica is 1 (15-100).
Optionally, the catalyst is at least one of nickel, iron, cobalt simple substance and alloy thereof. The average particle diameter D50 of the catalyst is 10-300 nm.
Optionally, in the step (2), the growing process of the carbon nanotube includes: uniformly mixing the porous silicon monoxide with a catalyst, introducing a gaseous carbon source at the cracking temperature of 200-1800 ℃ in the presence of protective gas to perform a cracking reaction for 1-10h, stopping introducing the gaseous carbon source, and continuing introducing the protective gas to cool to obtain the carbon nano tube. Preferably, the cracking temperature is 500-.
Further, the means for uniformly mixing the catalyst and the porous-structured silica includes mechanical fusion or ball milling. The particles of the catalyst can be uniformly dispersed on the surfaces of the particles of the porous silicon oxide by mechanical fusion or ball milling mixing, and partially enter the inside of the holes. Optionally, the rotation speed of the mechanical fusion is 1000-. Optionally, the ball milling is performed by taking one or more of zirconia, agate and alumina as a ball milling medium, the ball-to-material ratio is controlled to be 1: 1-20: 1, the rotation speed of the ball milling is 100-600rpm, and the ball milling time is 2-40 h. Preferably, the time of ball milling is 5 to 30 hours.
Further, in the process of growing the carbon nano tube, the temperature rise rate reaching the cracking temperature is 0.1-20 ℃/min. The protective gas is at least one of nitrogen, argon and helium; the gaseous carbon source is at least one of gaseous hydrocarbons such as methane, acetylene, ethylene, propylene and the like.
In the invention, the carbon nano tube generated in situ can be a single-wall carbon nano tube or a multi-wall carbon nano tube, and the length-diameter ratio of the carbon nano tube is not less than 3000. Preferably 3000-. The introduced carbon nano tube with high length-diameter ratio can effectively improve the conductivity of the material, and can be wound on the outer surface of the final product silicon-based composite negative electrode material in the following step (4) to form a cage structure, so that the volume expansion of the internal silicon monoxide generated in the charging and discharging process can be inhibited to a certain extent.
In the step (2), the in-situ grown carbon nano tube can be firmly combined with the porous silicon monoxide, so that the conductivity of the silicon monoxide is obviously improved; the carbon nanotubes distributed on the monox from inside to outside can also increase the transmission channels of lithium ions and electrons, improve the multiplying power performance and increase the capacity.
Further, the mass ratio of the carbon nano tube to the porous-structure-containing silicon monoxide is 1 (50-1000).
Optionally, in the step (3), the carbon coating by using a chemical vapor deposition method includes: and (3) placing the material obtained in the step (2) in a tubular furnace, introducing inert gas, heating to 100-300 ℃ at the heating rate of 1-20 ℃/min, introducing an organic carbon source, heating to 400-700 ℃ at the heating rate of below 5 ℃/min, preserving heat for 0.5-8h, and cooling to below 50 ℃ along with the furnace to obtain a gas-phase coated product.
The inert gas is at least one of nitrogen, argon and helium, and the organic carbon source is at least one of methane, acetylene, propylene, toluene, benzene, xylene, methanol, ethanol, propanol, butanol, pentanol, acetone, butanone, 2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate and amyl acetate. Wherein, when the organic carbon source is liquid at normal temperature, inert gas can be used for introducing the organic carbon source into the tubular furnace. Further, the organic carbon source is a mixture of at least one of benzene and xylene and at least one of methanol, ethanol, propanol, butanol and pentanol. Preferably, the flow rate of the organic carbon source is 1-100mL/min, and the flow rate of the inert gas is 5-600 mL/min.
Optionally, the thickness of the first carbon coating layer is 1-50 nm. The thickness of the first carbon coating layer is controlled by regulating the flow rate of the inert gas and the dosage of the organic carbon source.
In the step (3), the first carbon coating layer obtained by CVD is compact and uniform, has proper thickness, can effectively inhibit the volume expansion of the core silicon monoxide, can avoid the direct contact of the silicon monoxide and electrolyte, reduces the lithium loss in the battery cycle process and improves the cycle performance of the material.
Optionally, in the step (4), the solid content of the mixed slurry is 10-50%.
In the invention, in the mixed slurry, the mass ratio of the material obtained in the step (3) to the graphite, the conductive agent and the binder is 100: (1-20): (0.5-5):(1-10). The mass ratio is favorable for forming a firm and compact second coating layer with certain elasticity and good conductivity, so that the graphite and the conductive agent are uniformly distributed in the second coating layer, the influence of the introduction of inactive substances on the integral specific capacity of the silicon-based composite negative electrode material can be reduced to the greatest extent, and the capacity reduction is avoided.
Wherein, the stirring speed adopted in the preparation process of the mixed slurry is 1000-3000 rpm. The stirring at the rotating speed is more beneficial to the uniform dispersion of all raw materials.
Alternatively, the conductive agent may include at least one of conductive carbon black (specifically, acetylene black, ketjen black, super P, 350G carbon black), furnace black, and may further include other conductive particles. Wherein the graphite is at least one of natural graphite (such as crystalline flake graphite and expanded graphite), artificial graphite (such as KS-6), spherical graphite and three-dimensional graphite sponge.
Optionally, the graphite has a D50 particle size of 0.5-2 μm; the D50 particle size of the conductive agent is 100-300 nm. The graphite and the conductive agent with the grain sizes can be stably attached to the porous silicon oxide surface which is coated by the first carbon coating layer and is grown with the carbon nano tubes.
Optionally, the binder comprises at least one of sodium carboxymethylcellulose (CMC), sodium alginate, polypyrrole, a polythiophene and epoxy mixture, a polythiophene and polyurethane mixture, polyaniline, cellulose, polytetrafluoroethylene, polychlorotrifluoroethylene, polymethacrylamide, polyvinylidene chloride.
Wherein the solvent is selected from one or more of water, ethanol, ethylene glycol, isopropanol, isobutanol, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, N-methylpyrrolidone (NMP), and N, N-Dimethylformamide (DMF), but is not limited thereto.
Wherein the inlet temperature of the spray drying granulation is 180-300 ℃, and the outlet temperature is 80-120 ℃. The temperature range can cause the adhesive to generate a crosslinking reaction to generate an adhesive coating film.
In the spray drying process in the step (4), the binder is crosslinked/polymerized under the heating action of spray drying to form a binder film, and high-conductivity substances such as flake graphite and conductive agent particles are embedded therein, which together form a second coating layer. The second coating layer has good elasticity and conductivity, can further inhibit the volume expansion of the inner core of the silica, keeps the stability of the structure of the second coating layer, and can increase the electric contact between the silicon-based composite negative electrode materials, increase the lithium ion transmission rate between the silicon-based composite negative electrode materials and further improve the multiplying power performance of the silicon-based composite negative electrode materials. The granular conductive agent and part of the carbon nano tubes grown in the granular conductive agent can supplement the coating of the flake graphite outside the first carbon coating layer, so that a coating structure with uniform conductivity and stable structure is formed.
The preparation method provided by the first aspect of the invention is simple to operate, high-temperature sintering treatment is not carried out in the whole process, the core silicon material is well kept in an initial amorphous state, and the production cost can be effectively reduced. The preparation method is suitable for large-scale industrial production. The final product silicon-based composite negative electrode material has a multilayer coating structure, each layer of coating is compact, and the carbon nano tubes with large length-diameter ratio penetrate through the inner layer and the outer layer of the particles, so that the conductivity in the particles and among different particles is good; the silicon-based composite negative electrode material has an unobvious volume expansion effect in the battery charging and discharging processes, and has good cycle stability.
In a second aspect, the invention also provides a silicon-based composite negative electrode material, which sequentially comprises an inner core, a first coating layer and a second coating layer from inside to outside, wherein the inner core is silicon monoxide with a porous structure, and carbon nanotubes grow in situ on the surface and in the pores of the inner core; the first coating layer is a pyrolytic carbon layer, the second coating layer comprises an adhesive film, and graphite and a conductive agent which are embedded in the adhesive film, wherein part of the carbon nanotubes penetrate out of the second coating layer.
Optionally, the silicon-based composite anode material is prepared by the preparation method of the first aspect of the invention.
Optionally, the graphite and the conductive agent are exposed on the surface of the second coating layer. This may further increase the electrical contact between the silicon-based composite anode material.
Optionally, the carbon nanotubes are wound into a cage structure outside the second coating layer.
Optionally, the thickness of the first cladding layer is 1-50 nm. Preferably 1-10 nm.
Optionally, the thickness of the second cladding layer is 0.5-2 μm. Preferably 1-2 μm.
Optionally, the particle size of the silicon-based composite anode material is 5-30 μm. Preferably 5-20 μm.
Optionally, the tap density of the silicon-based composite anode material is 0.5-1.5g/cm3。
The silicon-based composite negative electrode material has a multilayer coating structure, is stable in structure and good in conductivity, and can be used for preparing a battery, and the initial amorphous state of the inner core oxidized silicon monoxide is kept. Such as the preparation of lithium ion batteries. The first charge specific capacity of the lithium ion battery prepared from the silicon-based composite negative electrode material is more than 1000 mAh.g under the discharge rate of 0.1C-1The first coulombic efficiency is not lower than 86%, and the coulombic efficiency of the 100 th cycle is more than 90%.
In a third aspect, the invention further provides a lithium ion battery, which comprises the silicon-based composite anode material in the second aspect.
In the third aspect of the invention, the lithium ion battery prepared from the silicon-based composite negative electrode material has high capacity and rate capability, shows good circulation stability, and can avoid the defect of volume expansion of silicon materials.
Drawings
Fig. 1 is a flow chart of a preparation process of a silicon-based composite anode material according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a silicon-based composite anode material prepared by the preparation method provided by an embodiment of the invention.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing a silicon-based composite anode material, including the following steps:
s01, corroding the silicon monoxide particles to obtain silicon monoxide with a porous structure;
s02, growing carbon nanotubes on the surface and in the pores of the porous silicon oxide in situ in the presence of a catalyst, and then carrying out acid washing to remove the catalyst; the mass ratio of the catalyst to the porous-structure-containing silicon monoxide is 1 (10-1000), and the length-diameter ratio of the carbon nanotube is not less than 3000;
s03, carrying out carbon coating on the material obtained in the step S02 by adopting a chemical vapor deposition method to form a first coating layer;
s04, preparing the material obtained in the step S03, graphite, a conductive agent, a binder and a solvent into mixed slurry; spray drying and granulating the mixed slurry, and forming a second coating layer in which the graphite and the conductive agent are embedded outside the first coating layer to obtain the silicon-based composite negative electrode material; wherein part of the carbon nanotubes are inserted from the second coating layer; the mass ratio of the material obtained in the step S03 to the graphite, the conductive agent and the binder is 100: (1-20): (0.5-5):(1-10).
The structural schematic diagram of the silicon-based composite anode material obtained by the method is shown in fig. 2, the silicon-based composite anode material sequentially comprises an inner core, a first coating layer 30 and a second coating layer 40 from inside to outside, the inner core is silicon monoxide 1 with a porous structure, and carbon nanotubes 20 grow on the surface and in the holes 10 in situ. The first coating layer 30 is a pyrolytic carbon layer obtained by a CVD method, the second coating layer 40 includes a binder film 41 and graphite 42 and a conductive agent 43 embedded in the binder film 41, and the carbon nanotubes 20 are penetrated from the second coating layer 40. Alternatively, the carbon nanotube 20 may be wound outside the second cladding layer 40 to form a certain cage structure. The graphite 42 and the conductive agent 43 are exposed on the surface of the second cladding layer 40.
The following provides a further description of embodiments of the invention in terms of several examples.
Example 1
A preparation method of a silicon-based composite anode material comprises the following steps:
(1) adding amorphous silica with the average particle size D50 of 5 microns into a hydrofluoric acid solution with the mass concentration of 10%, carrying out corrosion reaction for 1h while carrying out ultrasonic stirring, carrying out suction filtration on the reaction mixture after the corrosion is finished, washing the solid obtained by the suction filtration by using pure water until the pH value of the washing liquid is 7, and then drying in a drying oven at 110 ℃ to obtain a porous silicon-based matrix, namely the silica with a porous structure;
(2) mechanically fusing iron powder with the particle size of 150nm and the porous silicon-based matrix according to the mass ratio of 1:99, wherein the rotating speed of a fusion machine is 4500rpm, and the fusion time is 10min, so as to obtain a compound with the iron powder uniformly distributed on the surface and in the pores of the porous silicon-based matrix;
transferring the obtained compound to a CVD tube furnace for growing the carbon nano tube, introducing nitrogen at the flow rate of 0.1L/min, heating to 700 ℃ at the heating rate of 5 ℃/min, carrying out heat treatment for 1h, then introducing carbon source gas ethylene at the flow rate of 0.05L/min for carrying out vapor deposition, stopping introducing the carbon source gas after depositing for 4h, continuously introducing the nitrogen at the flow rate of 0.1L/min, keeping for 6h, then stopping introducing the nitrogen, and naturally cooling to below 50 ℃ to obtain the porous silicon oxide with the carbon nano tube, wherein the carbon nano tube is distributed on the surface and in the hole of the porous silicon oxide, the length-diameter ratio of the carbon nano tube is more than 4000, and the mass ratio of the carbon nano tube to the silicon oxide with the porous structure is 1: 100;
(3) transferring the material in the step (2) into a CVD (chemical vapor deposition) tube furnace, introducing argon, heating to 280 ℃ at a heating rate of 10 ℃/min, then beginning to introduce an ethanol solution with the mass fraction of toluene of 5%, simultaneously reducing the heating rate of the furnace to 5 ℃/min, heating to 600 ℃, preserving heat for 4h, naturally cooling to below 50 ℃, taking out, and forming a pyrolytic carbon coating layer with the thickness of 3-5nm on the porous silicon oxide with the carbon nano tubes to obtain the silicon-based material coated with the pyrolytic carbon;
(4) adding the material obtained in the step (3), artificial graphite with the average particle size of 0.5 mu m, conductive carbon black with the average particle size of 0.2 mu m and sodium carboxymethyl cellulose (CMC) into pure water according to the mass ratio of 100:5:2:5, uniformly stirring at the rotating speed of 2000rpm to obtain mixed slurry with the solid content of 30%, carrying out spray drying on the obtained mixed slurry, controlling the inlet temperature at 260 ℃ and the outlet temperature at 110 ℃ during spray drying, and forming a second coating layer with the thickness of 1.3-1.8 mu m on the surface of the pyrolytic carbon layer to obtain a crude product;
(5) adding the crude product into aqua regia (mixed acid liquor with the volume ratio of concentrated hydrochloric acid to concentrated nitric acid being 3: 1), heating to maintain the temperature of the solution above 95 ℃, stirring for 4 hours to remove the iron powder, then carrying out suction filtration, washing the obtained solid with pure water until the pH value of the washing liquor is 7, drying in a drying oven at 110 ℃, and sieving with a 200-mesh sieve to obtain the silicon-based composite negative electrode material with the average particle size of about 6.5 mu m.
Example 2
A preparation method of a silicon-based composite anode material comprises the following steps:
(1) adding amorphous silica with the average particle size D50 of 5 microns into a hydrofluoric acid solution with the mass concentration of 20%, carrying out corrosion reaction for 0.5h while carrying out ultrasonic stirring, after the corrosion is finished, carrying out suction filtration on the reaction mixture, washing the solid obtained by the suction filtration by using pure water until the pH value of the washing liquid is 7, and then drying in a 110 ℃ oven to obtain a porous silicon-based substrate, namely the silica with a porous structure.
(2) Mechanically fusing a catalyst (specifically a mixture of iron powder and nickel powder) with the particle size of 100nm and the porous silicon-based matrix according to the mass ratio of 3:97, wherein the rotating speed of a fusion machine is 3500rpm, and the fusion time is 20min, so as to obtain a compound in which catalyst powder is uniformly distributed on the surface and in the pores of the porous silicon-based matrix;
transferring the obtained compound to a CVD tube furnace for growing the carbon nano tube, firstly introducing nitrogen at the flow rate of 0.1L/min, heating to 600 ℃ at the heating rate of 10 ℃/min, carrying out heat treatment for 1.5h, then introducing carbon source gas acetylene at the flow rate of 0.05L/min for carrying out vapor deposition, stopping introducing the carbon source gas after 6h of deposition, continuously introducing the nitrogen at the flow rate of 0.1L/min, keeping for 6h, then stopping introducing the nitrogen, and naturally cooling to below 50 ℃ to obtain a porous crude product of the silicon monoxide with the carbon nano tube;
then adding the porous silicon monoxide crude product with the carbon nano tube into aqua regia (mixed acid liquor with the volume ratio of concentrated hydrochloric acid to concentrated nitric acid being 3: 1), heating to maintain the temperature of the solution above 95 ℃, stirring for 4 hours to remove the catalyst powder, then carrying out suction filtration, washing the obtained solid with pure water until the pH value of the washing liquor is 7, and drying in an oven at 110 ℃;
(3) transferring the material purified in the step (2) to a CVD (chemical vapor deposition) tube furnace, introducing argon, heating to 300 ℃ at a heating speed of 5 ℃/min, then beginning to introduce an ethanol solution with the mass fraction of xylene being 5%, simultaneously reducing the heating rate of the furnace to 3 ℃/min, heating to 600 ℃, preserving the temperature for 5h, naturally cooling to below 50 ℃, taking out, and forming a pyrolytic carbon coating layer with the thickness of 5-8nm on the porous silicon oxide with the carbon nano tubes to obtain the silicon-based material coated with the pyrolytic carbon;
(4) adding the material obtained in the step (3), artificial graphite with the average particle size of 1 micrometer, conductive carbon black with the average particle size of 0.5 micrometer and sodium alginate into pure water according to the mass ratio of 100:5:3:5, uniformly stirring at the rotating speed of 2000rpm to obtain mixed slurry with the solid content of 10%, carrying out spray drying on the obtained mixed slurry, controlling the inlet temperature at 280 ℃ and the outlet temperature at 110 ℃ during spray drying, and sieving by using a 200-mesh sieve to form a second coating layer with the thickness of 1.2-1.8 micrometers on the surface of the pyrolytic carbon layer, thereby obtaining the silicon-based composite negative electrode material with the average particle size of about 6.4 micrometers.
Example 3
A preparation method of a silicon-based composite anode material comprises the following steps:
(1) adding amorphous silica with the average particle size D50 of 10 microns into a NaOH solution with the mass concentration of 10%, carrying out corrosion reaction for 1h while carrying out ultrasonic stirring, carrying out suction filtration on a reaction mixture after corrosion is finished, washing a solid obtained by suction filtration by using pure water until the pH value of a washing liquid is 7, and then placing the solid in a 120 ℃ drying oven for drying to obtain a porous silicon-based matrix, namely the silica with a porous structure;
(2) mixing nickel powder with the particle size of 200nm and the porous silicon-based matrix by adopting a ball mill according to the mass ratio of 2:98, wherein the ball milling medium adopts zirconia balls with the diameter of 0.3mm, the ball material ratio is 2:1, the rotating speed of the ball mill is 100rpm, and the ball milling mixing time is 20 hours, so as to obtain a compound with nickel powder uniformly distributed on the surface and in the pores of the porous silicon-based matrix;
transferring the obtained compound to a CVD tube furnace for growing the carbon nano tube, introducing nitrogen at the flow rate of 0.1L/min, heating to 800 ℃ at the heating rate of 1 ℃/min, carrying out heat treatment for 0.5h, then introducing carbon source gas propylene at the flow rate of 0.05L/min for vapor deposition, stopping introducing the carbon source gas after deposition for 3h, continuously introducing nitrogen at the flow rate of 0.1L/min, keeping for 6h, stopping introducing the nitrogen, and naturally cooling to below 50 ℃ to obtain porous silicon monoxide with the carbon nano tube; the carbon nano tubes are distributed on the surface and in the pores of the porous silicon oxide, the length-diameter ratio of the carbon nano tubes is larger than 5000, and the mass ratio of the carbon nano tubes to the porous silicon oxide is 1: 200;
(3) transferring the material in the step (2) into a CVD (chemical vapor deposition) tube furnace, introducing argon, heating to 300 ℃ at a heating rate of 10 ℃/min, then beginning to introduce an ethanol solution with the mass fraction of toluene of 5%, simultaneously reducing the heating rate of the furnace to 2 ℃/min, heating to 650 ℃, preserving heat for 6h, naturally cooling to below 50 ℃, taking out, and forming a pyrolytic carbon coating layer with the thickness of about 15nm on the porous silicon oxide with the carbon nano tubes to obtain the silicon-based material coated with the pyrolytic carbon;
(4) adding the material obtained in the step (3), artificial graphite with the average particle size of 0.5 mu m, conductive carbon black with the average particle size of 0.5 mu m and polymethacrylamide into pure water according to the mass ratio of 100:4:4:5, uniformly stirring at the rotating speed of 2000rpm to obtain mixed slurry with the solid content of 20%, carrying out spray drying on the obtained mixed slurry, controlling the inlet temperature at 250 ℃ and the outlet temperature at 100 ℃ during spray drying, and forming a second coating layer with the thickness of about 1.2-2 mu m on the surface of the pyrolytic carbon layer to obtain a crude product;
(5) adding the crude product into aqua regia (mixed acid liquor with the volume ratio of concentrated hydrochloric acid to concentrated nitric acid being 3: 1), heating to maintain the temperature of the solution above 95 ℃, stirring for 4 hours to remove the iron powder, then carrying out suction filtration, washing the obtained solid with pure water until the pH value of the washing liquor is 7, drying in a drying oven at 110 ℃, and sieving with a 200-mesh sieve to obtain the silicon-based composite negative electrode material with the average particle size of about 11.8 mu m.
To highlight the advantageous effects of the present invention, the following comparative examples 1 to 3 were provided.
Comparative example 1
A preparation method of a silicon-based composite anode material comprises the following steps:
(1) adding amorphous silica with the average particle size D50 of 5 microns into a hydrofluoric acid solution with the mass concentration of 10%, carrying out corrosion reaction for 1h while carrying out ultrasonic stirring, carrying out suction filtration on the reaction mixture after the corrosion is finished, washing the solid obtained by the suction filtration by using pure water until the pH value of the washing liquid is 7, and then drying in a drying oven at 110 ℃ to obtain a porous silicon-based matrix, namely the silica with a porous structure;
(2) adding the porous silicon-based matrix obtained in the step (1), artificial graphite with the average particle size of 0.5 mu m, conductive carbon black with the average particle size of 0.5 mu m and sodium carboxymethyl cellulose (CMC) into pure water according to the mass ratio of 100:5:2:5, uniformly stirring at the rotating speed of 2000rpm to obtain mixed slurry with the solid content of 30%, carrying out spray drying on the obtained mixed slurry, controlling the inlet temperature at 260 ℃ and the outlet temperature at 110 ℃ during spray drying, and sieving to obtain the silicon-based composite negative electrode material, wherein the inner core of the silicon-based composite negative electrode material is silica with a porous structure, and the outer shell of the silicon-based composite negative electrode material is a composite coating layer formed by a CMC film, graphite embedded in the CMC film and the conductive carbon black.
Comparative example 2
A preparation method of a silicon-based composite anode material comprises the following steps:
(1) adding amorphous silica with the average particle size D50 of 5 microns into a hydrofluoric acid solution with the mass concentration of 10%, carrying out corrosion reaction for 1h while carrying out ultrasonic stirring, carrying out suction filtration on the reaction mixture after the corrosion is finished, washing the solid obtained by the suction filtration by using pure water until the pH value of the washing liquid is 7, and then drying in a drying oven at 110 ℃ to obtain a porous silicon-based matrix, namely the silica with a porous structure;
(3) transferring the porous silicon-based substrate to a CVD (chemical vapor deposition) tube furnace, introducing argon, heating to 280 ℃ at a heating rate of 10 ℃/min, then beginning to introduce an ethanol solution with the mass fraction of toluene of 5%, simultaneously reducing the heating rate of the furnace to 5 ℃/min, heating to 600 ℃, preserving heat for 4h, naturally cooling to below 50 ℃, taking out, and forming a pyrolytic carbon coating layer on the surface of the porous silicon oxide;
(3) mechanically fusing iron powder with the particle size of 150nm and the material obtained in the step (2) according to the mass ratio of 5:95, wherein the rotating speed of a fusion machine is 4500rpm, and the fusion time is 10 min;
transferring the fused mixture to a CVD tube furnace for growing carbon nano tubes, introducing nitrogen at the flow rate of 0.1L/min, heating to 300 ℃ at the heating rate of 0.1 ℃/min, carrying out heat treatment for 1h, introducing carbon source gas ethylene at the flow rate of 0.05L/min for vapor deposition, stopping introducing the carbon source gas after deposition for 4h, continuously introducing nitrogen at the flow rate of 0.1L/min, keeping for 6h, stopping introducing the nitrogen, naturally cooling to below 50 ℃, and generating CNT on the outer surface of pyrolytic carbon in situ to obtain porous silicon monoxide coated by the CNT and the pyrolytic carbon in a composite manner;
(4) adding the material obtained in the step (3), artificial graphite with the average particle size of 0.5 mu m, conductive carbon black with the average particle size of 0.5 mu m and sodium carboxymethyl cellulose (CMC) into pure water according to the mass ratio of 100:5:2:5, uniformly stirring at the rotating speed of 2000rpm to obtain mixed slurry with the solid content of 30%, carrying out spray drying on the obtained mixed slurry, controlling the inlet temperature at 260 ℃ and the outlet temperature at 110 ℃ during spray drying, and forming a second coating layer on the surface of the pyrolytic carbon layer to obtain a crude product;
(5) adding the crude product into aqua regia (mixed acid liquor with the volume ratio of concentrated hydrochloric acid to concentrated nitric acid being 3: 1), heating to maintain the temperature of the solution above 95 ℃, stirring for 4 hours to remove the iron powder, then carrying out suction filtration, washing the obtained solid with pure water until the pH value of the washing liquor is 7, drying in a drying oven at 110 ℃, and sieving with a 200-mesh sieve to obtain the silicon-based composite negative electrode material.
Comparative example 3
A method for preparing a silicon-based composite anode material, which is different from the method in example 1 in that: the etching pore-forming operation in step (1) was not carried out, but the operations in steps (2) to (5) in example 1 were carried out by using silica having an average particle diameter D50 of 5 μm as it is.
Application examples
In order to test the performance of the silicon-based composite negative electrode material prepared by the method, the silicon-based composite negative electrode material is respectively prepared into half batteries and then tested, and the method specifically comprises the following steps: (1) mixing a silicon-based composite negative electrode material with a conductive agent Super-P, LA133 series adhesive according to a mass ratio of 94.5:2:3.5, adding water to form uniformly mixed negative electrode slurry, coating the negative electrode slurry on the surface of copper foil, rolling to a certain thickness, and performing vacuum drying for 8 hours at 110 ℃ to prepare a negative electrode plate;
(2) adopts a metal lithium sheet as a counter electrode and a polypropylene microporous membrane as a diaphragm, and 1.0mol/L LiPF6Ethylene Carbonate (EC): and (3) taking a solution of dimethyl carbonate (DMC) in a volume ratio of 1: 1-5 as an electrolyte, and assembling the solution into a CR2032 button half-cell in a glove box according to the sequence of a positive electrode shell, a negative electrode plate, a diaphragm, a lithium plate, a stainless steel gasket, a stainless steel elastic sheet and a negative electrode shell.
And (3) placing each assembled half cell at room temperature for 6h, and then carrying out charge and discharge tests, wherein the charge and discharge voltage range is 0.01V-1.5V, the charge and discharge rate is 0.1C, and the test results are shown in Table 1.
Table 1 summary of the properties of half-cells made from silicon-based composite anode materials of different examples
Figure BDA0002472907140000141
In table 1, the silicon-based composite negative electrode material of comparative example 1 has no CVD coating layer, and graphite, a conductive agent, and a binder are directly used to perform liquid phase coating on the porous silicon oxide, so that the formed coating layer is not dense enough, which causes direct contact between the internal silicon matrix material and an electrolyte, and an SEI film generated on the surface of the material is continuously destroyed and reformed along with the change of the volume of the SEI film, thereby consuming a large amount of lithium ions, and causing poor battery cycle.
In the preparation of the silicon-based composite negative electrode material of the comparative example 2, the CVD carbon coating is performed, and then the carbon tube is grown in situ, which reduces the porosity of the silicon-based composite negative electrode material too much, and the grown carbon tube is less, thereby reducing the direct contact between the silicon-based composite negative electrode material and the carbon tube, deteriorating the conductivity of the material, and simultaneously, the distance of lithium ions in the electrolyte transmitted into the silicon-based composite negative electrode material is lengthened, and the rate capability is weakened.
In the preparation of the silicon-based composite anode material of the comparative example 3, no pore-forming is performed on the silicon monoxide, so that the specific surface area of the material is small, and the in-phase conductivity is poor; and the material does not have micropores as a buffer for volume expansion, so that the material is easy to break and pulverize, and the cycle performance of the battery is poor.
As can be seen from table 1, the lithium ion half-cell made of the silicon-based composite negative electrode material prepared by the method provided by the invention has large first charge specific capacity and first discharge specific capacity, and the cycle performance of the cell is good, the capacity retention rate after 100 cycles is still over 90%, and the overall performance is more excellent compared with the silicon-based composite negative electrode material prepared by comparative examples 1-3.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The preparation method of the silicon-based composite anode material is characterized by comprising the following steps of:
(1) corroding the silicon monoxide particles to obtain silicon monoxide with a porous structure;
(2) uniformly mixing a catalyst and the porous-structure silicon monoxide, and growing carbon nanotubes on the surface and in the pores of the porous-structure silicon monoxide in situ, wherein the mass ratio of the catalyst to the porous-structure silicon monoxide is 1 (32.3-1000), and the length-diameter ratio of the carbon nanotubes is not less than 3000;
(3) performing carbon coating on the material obtained in the step (2) by adopting a chemical vapor deposition method to form a first coating layer; wherein the first coating layer is a pyrolytic carbon layer;
(4) preparing the material obtained in the step (3) with graphite, a granular conductive agent, a binder and a solvent into mixed slurry, wherein the mass ratio of the material obtained in the step (3) to the graphite, the granular conductive agent and the binder is 100: (1-20): (0.5-5): 1-10);
carrying out spray drying granulation on the mixed slurry, and forming a second coating layer in which the graphite and the granular conductive agent are embedded outside the first coating layer to obtain the silicon-based composite negative electrode material; wherein the second coating layer comprises an adhesive film formed by crosslinking/polymerizing the adhesive under the heating action of the spray-drying granulation; and part of the carbon nanotubes penetrate out of the second coating layer and are wound outside the second coating layer to form a cage structure.
2. The method of claim 1, further comprising: after the carbon nanotubes are grown in situ in step (2) or after the spray drying granulation, acid washing is performed to remove the catalyst.
3. The production method according to claim 1, wherein the pore size of the porous-structured silica is 10 to 300 nm.
4. The method of claim 1, wherein the uniformly mixing of the catalyst and the porous silica comprises mechanical fusion or ball milling.
5. The method according to claim 4, wherein the rotation speed of the mechanical fusion is 1000-5000rpm, and the time of the mechanical fusion is 1-120 min; the rotation speed of the ball milling is 100-600rpm, and the ball milling time is 2-40 h.
6. The method of claim 1, wherein the binder comprises at least one of sodium carboxymethylcellulose, sodium alginate, polypyrrole, a mixture of polythiophene and epoxy resin, a mixture of polythiophene and polyurethane, polyaniline, cellulose, polytetrafluoroethylene, polychlorotrifluoroethylene, polymethacrylamide, and polyvinylidene chloride; the granular conductive agent comprises at least one of conductive carbon black and furnace black.
7. The method of claim 1, wherein the graphite has a D50 particle size of 0.5 to 2 μm; the D50 particle size of the granular conductive agent is 100-300 nm.
8. A silicon-based composite anode material prepared by the preparation method according to any one of claims 1 to 7, wherein the silicon-based composite anode material comprises an inner core, a first coating layer and a second coating layer from inside to outside in sequence, the inner core is silica with a porous structure, and carbon nanotubes grow in situ on the surface and in the pores of the inner core; the first coating layer is a pyrolytic carbon layer, the second coating layer comprises an adhesive film, graphite and a granular conductive agent embedded into the adhesive film, and partial carbon nanotubes are inserted out of the second coating layer and wound outside the second coating layer to form a cage structure.
9. The silicon-based composite anode material according to claim 8, wherein the thickness of the first coating layer is 1-50nm, and the thickness of the second coating layer is 0.5-2 μm.
10. A lithium ion battery comprising the silicon-based composite anode material according to any one of claims 8 to 9.
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