CN112635733A - Negative electrode material of lithium ion battery, preparation method of negative electrode material and lithium ion battery - Google Patents

Negative electrode material of lithium ion battery, preparation method of negative electrode material and lithium ion battery Download PDF

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CN112635733A
CN112635733A CN202011516545.XA CN202011516545A CN112635733A CN 112635733 A CN112635733 A CN 112635733A CN 202011516545 A CN202011516545 A CN 202011516545A CN 112635733 A CN112635733 A CN 112635733A
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temperature
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negative electrode
graphite
treatment
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CN112635733B (en
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乔帅帅
郑加镇
江宏富
吴亚娟
燕靖
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Jiangsu Jixin Semiconductor Silicon Research Institute Co Ltd
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Jiangsu Jixin Semiconductor Silicon Research Institute 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
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    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • 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
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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    • 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 negative electrode material of a lithium ion battery, a preparation method of the negative electrode material and the lithium ion battery. The method comprises the following steps: obtaining a composite material precursor, and calcining to obtain a composite material; depositing to form silicon particles on the conductive framework of the composite material by using chemical vapor deposition, wherein the chemical vapor deposition is realized in a fluidized bed reactor by adopting a silane-hydrogen-inert gas three-component reaction system; and carrying out carbon coating treatment on the composite material with the silicon particles to form the negative electrode material. The silicon-carbon composite material, namely the cathode material prepared by the method has the characteristics of good cycle stability, high capacity retention rate, good conductivity and the like.

Description

Negative electrode material of lithium ion battery, preparation method of negative electrode material and lithium ion battery
Technical Field
The invention relates to the field of materials, in particular to a negative electrode material of a lithium ion battery, a preparation method of the negative electrode material and the lithium ion battery.
Background
The negative electrode material of the lithium ion battery is an important component of the lithium battery midstream industry, and the performance of the negative electrode material also has a decisive influence on the performance of the lithium ion battery. At present, the negative electrode material mainly made of graphite has the advantages of price advantage, higher matching degree with the current positive electrode and electrolyte, and the like. However, the specific capacity of the current graphite negative electrode material is about to approach the theoretical limit, and the space for continuously improving the specific capacity is limited, so that the requirement of a high-energy density battery is difficult to meet.
Silicon is considered as a next-generation high-energy-density lithium ion battery cathode material, but the conductivity of the silicon is low, and a severe volume effect (expansion rate is more than 300%) exists in the charging and discharging process, so that the particles are crushed, and a solid electrolyte layer (SEI film) on the surface of the particles is repeatedly formed, thereby causing the problems of capacity loss, poor cycle performance and the like, and greatly limiting the application of the silicon in the lithium ion battery. Although the problems of volume expansion, low conductivity and the like of silicon in the charging and discharging processes can be reduced by forming a composite material through technologies such as nanocrystallization and carbon coating, the negative electrode material of an ion battery, a preparation method thereof and the lithium ion battery still need to be improved.
Disclosure of Invention
In view of the above, the present invention is directed to a method for preparing a negative electrode material for a lithium ion battery, and a method for preparing the negative electrode material, so as to improve the conductivity of a silicon-based negative electrode material, alleviate the volume expansion, and improve the cycle performance and the capacity loss.
In one aspect of the invention, a method of preparing an anode material for a lithium ion battery is presented. The method comprises the following steps: mixing silicon oxide, graphite and a conductive polymer to form slurry, and drying and granulating to obtain a composite material precursor; calcining the composite material precursor to obtain a composite material; depositing to form silicon particles on the conductive framework of the composite material by using chemical vapor deposition, wherein the chemical vapor deposition is realized in a fluidized bed reactor by adopting a silane-hydrogen-inert gas three-component reaction system; and carrying out carbon coating treatment on the composite material with the silicon particles to form the negative electrode material. According to the invention, silicon with nanometer size is deposited on the surface, pores and a conductive polymer framework of the prepared graphite by a silane-hydrogen-inert gas three-component gas phase deposition process to form silicon with nanometer size and perform carbon coating, so that the stability of a silicon-carbon interface can be further enhanced, the nano silicon is dispersed on the conductive framework more uniformly, the carbon coating is complete and has better strength, the compatibility problem of the nano silicon and an electrolyte is improved, and a stable SEI film is favorably formed. The porous loose structure of graphite and conductive polymer, such as polyaniline, improves the lithium ion transmission performance and can provide a buffer effect for the volume expansion effect of the nano silicon in the charge-discharge process. And the introduction of the high molecular conductive polymer further improves the conductivity of the material. In conclusion, the silicon-carbon composite material, namely the cathode material prepared by the method has the characteristics of good cycle stability, high capacity retention rate, good conductivity and the like.
According to an embodiment of the present invention, obtaining the composite material precursor includes: mixing the silicon oxide, graphite, conductive polymer and organic solvent, sanding, and drying and granulating the sanded slurry, wherein the drying process comprises centrifugal or air-flow spray drying. Thus, a composite precursor mixed uniformly can be obtained.
According to an embodiment of the present invention, the graphite comprises one of natural graphite, artificial graphite, and spheroidal graphite, preferably spheroidal graphite. Thereby, the performance of the anode material obtained by the method can be further improved.
According to the embodiment of the invention, the particle size of the graphite is 5-20 μm. Thereby, a skeleton structure more suitable for lithium ion intercalation and deintercalation is advantageously formed.
According to an embodiment of the present invention, the silicon oxide is SiOxWherein 0 is<x is less than or equal to 1, and the particle size of the silicon oxide is 0.1-0.2 mu m. Thereby, the performance of the anode material obtained by the method can be further improved.
According to an embodiment of the present invention, the organic solvent comprises one or more of absolute ethanol, acetone, benzene, N-methylpyrrolidone. This makes it possible to form a slurry having a better dispersibility.
According to the embodiment of the invention, the rotation speed of the sanding treatment is 800-1200 r/min, the sanding time is 4-10 h, and the solvent amount during the sanding treatment is 40-70 parts by weight; the drying treatment is airflow type spray drying, the air inlet temperature of the drying treatment is 110-230 ℃, the air exhaust temperature is 70-90 ℃, and the slurry treatment capacity is 5-10L/h. Thereby, the performance of the anode material obtained by the method can be further improved.
According to the embodiment of the invention, the slurry further comprises an additive, and the ratio of the silicon oxide, the graphite, the polyaniline and the additive in parts by weight is (5-15): (30-60): (5-11): (1-7). Thereby, the performance of the anode material obtained by the method can be further improved.
According to an embodiment of the present invention, the additive comprises one or more of polyethylene glycol, sodium carboxymethylcellulose, sodium alginate, non-ionic polyvinylpyrrolidone, polyacrylic acid. Thereby, the performance of the anode material obtained by the method can be further improved.
According to the embodiment of the invention, the calcination treatment of the composite material precursor is carried out in an inert atmosphere, the temperature rise rate of the calcination treatment is 2-8 ℃/min, and the calcination treatment comprises the following steps: keeping the temperature at 200-400 ℃ for 2-4 h, heating to a target temperature, keeping the temperature for 3-6 h, wherein the target temperature is 1100-1600 ℃, and then cooling to room temperature. Thereby, the performance of the anode material obtained by the method can be further improved.
According to the embodiment of the invention, after the calcination treatment, the composite material precursor subjected to the calcination treatment is further subjected to acid washing, washing and drying. Thereby, the performance of the anode material obtained by the method can be further improved.
According to the embodiment of the invention, the solvent for acid cleaning is a mixed solution of hydrofluoric acid and hydrochloric acid, wherein the weight part of hydrofluoric acid is 90-99. This can further improve the effect of the pickling treatment.
According to the embodiment of the invention, the drying temperature is 60-150 ℃. Thereby, the performance of the anode material obtained by the method can be further improved.
According to an embodiment of the invention, the chemical vapor deposition comprises: and depositing the silicon particles on the surface, the inner part of the pores and the polyaniline skeleton of the graphite by using the composite material as a substrate by using a chemical vapor deposition method. Thereby, the performance of the anode material obtained by the method can be further improved.
According to an embodiment of the invention, the silicon particles are formed with a particle size of less than 100 nm. Thereby, the performance of the anode material obtained by the method can be further improved.
According to an embodiment of the invention, the chemical vapor deposition comprises: injecting silane into a fluidized bed reactor at a temperature lower than the self-decomposition temperature of the silane, simultaneously injecting hydrogen and inert gas at a temperature higher than the temperature of the silane, mixing the gases, and enabling the temperature of the gas mixture to be close to the reaction temperature, wherein the reaction temperature is 500-700 ℃. Thereby, the performance of the anode material obtained by the method can be further improved.
According to the embodiment of the invention, the inert gas comprises a gas which has the functions of absorbing infrared light and improving the thermal uniformity of the mixed gas; preferably, the inert gas comprises He, Ne, N2And Ar. Thereby, the performance of the anode material obtained by the method can be further improved.
According to the embodiment of the invention, the gas mixture introduced into the fluidized bed reactor is in a turbulent flow state, the residence time of the gas mixture is 5-66 s, and the total flow of gas is 1-2 mol/s. Thereby, the performance of the anode material obtained by the method can be further improved.
According to an embodiment of the present invention, the partial pressures of the gases in the three-component reaction system are: 1-70 kPa silane, 93-990 kPa hydrogen, 1-1000 kPa inert gas and 100-2000 kPa total pressure. Thereby, the performance of the anode material obtained by the method can be further improved.
According to the embodiment of the invention, in the silane-hydrogen subsystem, the molar fraction of the silane is 0.01-0.1;
according to the embodiment of the invention, the silicon loading amount in the material subjected to the chemical vapor deposition is 5-11 parts by weight. Thereby, the performance of the anode material obtained by the method can be further improved.
According to the embodiment of the invention, the carbon coating treatment is carried out by adopting a gas phase coating rotary furnace, and the air in the furnace is evacuated by using nitrogen before coating so that the oxygen content in the furnace is less than 0.1 ppm. Thereby, the performance of the anode material obtained by the method can be further improved.
According to an embodiment of the present invention, the carbon source gas used for the cladding process includes one of methane, ethylene or acetylene, and the carrier gas includes one of nitrogen or argon; the coating temperature in the furnace is 500-1000 ℃, the flow rate of the carbon source gas is 90-130 ml/min, the rotating speed of the furnace body is 0.5-5 r/min, and the retention time of the materials in the furnace at high temperature is 50-120 min. Thereby, the performance of the anode material obtained by the method can be further improved.
According to the embodiment of the invention, the content of the coated carbon in the anode material subjected to the coating treatment is 7-18 parts by weight.
In another aspect of the invention, the invention provides an anode material for a lithium ion battery. The anode material includes: a skeletal structure comprising graphite and a conductive polymer; silicon oxide located at least one of inside and on a surface of the skeletal structure; silicon particles, wherein the silicon particles are positioned on the framework structure, and the particle size of the silicon particles is not more than 100 nm. The cathode material has at least one of the advantages of good cycle stability, high capacity retention rate, good conductivity and the like.
According to an embodiment of the present invention, the anode material is prepared using the method described above. Therefore, the negative electrode material has all the characteristics and advantages of the negative electrode material obtained by the method, and the description is omitted.
In yet another aspect of the present invention, a lithium ion battery is presented. The lithium ion battery includes: the negative electrode comprises a negative electrode material, and the negative electrode material is the negative electrode material. Therefore, the lithium ion battery has all the characteristics and advantages of the cathode material obtained by the method, and the description is omitted.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 shows a schematic flow diagram of a method according to an embodiment of the invention;
fig. 2 shows a schematic structural diagram of a lithium ion battery according to an embodiment of the present invention.
Detailed Description
In the following, embodiments of the invention are described in detail, examples of which are illustrated in the accompanying drawings, wherein, without conflict, embodiments of the invention and features of the embodiments may be combined with each other. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
An object of the present invention is to provide a method for preparing a negative electrode material for a lithium ion battery, which, according to an embodiment of the present invention, uses a graphite-conductive polymer to form a conductive skeleton, thereby facilitating improvement of lithium ion transport properties, while providing a strong buffer for the volume expansion effect of a silicon-based material. And the nano-sized silicon is deposited on the surface, pores and the conductive polymer framework of the prepared graphite by a silane-hydrogen-inert gas three-component gas phase deposition process to form a carbon coating layer, so that the stability of a silicon-carbon interface can be enhanced, the nano-sized silicon is more uniformly dispersed on the conductive framework, the carbon coating layer is complete and has better strength, the compatibility problem of the nano-sized silicon and an electrolyte is improved, and a stable SEI film is favorably formed.
The inventor finds that the nanocrystallization of the silicon particles helps to release stress generated in the lithium intercalation and deintercalation process of the silicon negative electrode, and inhibits the occurrence of cracks and pulverization. The carbon-coated composite material can improve the electrical contact among negative electrode material particles, reduce the contact between the material and electrolyte, inhibit the overgrowth of an SEI film, stabilize an interface and provide certain buffer for the volume expansion of silicon. Compared with the method which singly adopts mechanical ball milling and high-temperature pyrolysis in the related technology of the silicon-carbon composite material, the method provided by the application can better form dispersed particles and prevent the particles from generating serious agglomeration. Compared with the silicon-carbon composite material prepared by a sol-gel method, the method provided by the application can better improve the conductivity of the cathode material and prevent the cathode material from structural fracture caused by cracking of an external coated carbon shell in the circulation process. In addition, the vapor deposition process adopting the three-component system of silane, hydrogen and inert gas can relieve or even solve the defects that the reaction gas needs to be excessively diluted and the reaction temperature is higher in the preparation of the nano-silicon by the traditional process, is favorable for optimizing process parameters and reduces the production cost.
The individual steps of the method are described in detail below, according to a specific embodiment of the invention. Referring to fig. 1, the method may include the steps of:
s100: forming slurry, drying and granulating to obtain the composite material precursor
According to the embodiment of the invention, in the step, silicon oxide, graphite and conductive polymer are mixed to form slurry, and the slurry is dried and granulated to obtain the composite material precursor.
Specifically, silicon oxide, graphite, a conductive polymer, and an organic solvent may be mixed and subjected to a sanding process, and the slurry subjected to the sanding process may be dried and granulated. Wherein the drying treatment comprises centrifugal or air-flow spray drying. Thus, a composite precursor mixed uniformly can be obtained.
The above-mentioned materials in the slurry according to the embodiment of the present invention are not particularly limited and may be selected by those skilled in the art according to practical circumstances. For example, the conductive polymer may include, but is not limited to, a high molecular polymer polymerized from monomers such as aniline, pyrrole, thiophene, and the like, and may be specifically polyaniline. The polyaniline can improve the conductivity of graphite on one hand, and is different from a doping mechanism that other conductive polymers generate cation vacancies under the action of an oxidant on the other hand, the number of electrons is not changed in the doping process of the polyaniline, and H is generated by the decomposition of doped protonic acid+And for anions (e.g. Cl)-Sulfate, phosphate, etc.) into the main chain, and combines with the N atoms in the amine and imine groups to form a polaron and a dipole delocalized into the P bond of the whole molecular chain, so that the polyaniline has higher conductivity. The unique doping mechanism enables doping and de-doping of polyaniline to be completely reversible, and the polyaniline can be more suitable for being applied to a negative electrode material of a lithium ion battery.
It should be specifically noted here that in the present invention, the conductive polymer is mixed with other components to form a paste, which is to be broadly understood as follows: the conductive polymer may be directly mixed with silicon oxide, graphite, or the like to form a slurry, or a conductive polymer monomer (such as the aforementioned aniline, thiophene, pyrrole, or the like) may be added to the slurry and polymerized under appropriate conditions to form a conductive polymer in a liquid slurry. Suitable conditions include, but are not limited to, adding an initiator to the slurry and polymerizing the monomers under polymerization conditions depending on the particular type of conductive polymer.
According to an embodiment of the present invention, the graphite may include one of natural graphite, artificial graphite, and spheroidal graphite, and particularly preferably may be spheroidal graphite. Thereby, the performance of the anode material obtained by the method can be further improved. The particle size of the graphite may be 5 to 20 μm. Thereby, a skeleton structure more suitable for lithium ion intercalation and deintercalation is advantageously formed.
According to an embodiment of the present invention, the silicon oxide is SiOxWherein 0 is<x is less than or equal to 1, and the particle size of the silicon oxide is 0.1-0.2 mu m. Thereby, the performance of the anode material obtained by the method can be further improved. Specifically, the volume expansion of the SiOx material is much smaller than that of the crystalline silicon material, and because the SiOx can generate lithium oxide LixO and lithium silicon compound during the first lithium insertion process, the high O content can cause more inactive substances to be generated during the reaction, and meanwhile, the generation of LixO and lithium silicon compound is an irreversible process, which causes the consumption of lithium source and the low first efficiency. On the premise of ensuring a certain capacity (2680 mAh/g of SiO and 4200mAh/g of Si) and first charging efficiency, SiO is added into the slurryxCan cooperate with the nano silicon particles of the subsequent chemical vapor deposition to form a conductive framework and SiOxThe composite structure of Si can reduce the size of the silicon oxide particles and even make the silicon oxide particles nano-sized by a treatment including but not limited to sanding when mixed to form a slurry, and can reduce the volume expansion as much as possible by compounding with nano-silicon, thereby improving the cycle performance of the composite material. Thereby being beneficial to relieving the volume expansion effect of the silicon-based cathode material.
According to the embodiment of the present invention, the specific type of the organic solvent is not particularly limited as long as the above-mentioned conductive polymer, graphite and SiO can be well dissolvedxAnd (4) finishing. For example, the organic solvent may include, but is not limited to, one or more of absolute ethanol, acetone, benzene, N-methylpyrrolidone. This makes it possible to form a slurry having a better dispersibility.
According to embodiments of the present invention, the mixed solution may be sanded to form a more uniform slurry. Specifically, the rotational speed of sanding treatment can be 800 ~ 1200r/min, and sanding time 4h ~ 10h, solvent amount when carrying out sanding treatment is 40 ~ 70 parts by weight. The raw materials in the slurry can be dispersed more uniformly after the sanding treatment. And then, drying and granulating the slurry to obtain the composite material precursor. Specifically, the drying treatment can be air-flow spray drying, the air inlet temperature is 110-230 ℃, the air exhaust temperature is 70-90 ℃, and the slurry treatment capacity is 5-10L/h. Thereby, the performance of the anode material obtained by the method can be further improved.
According to an embodiment of the present invention, the slurry may further include an additive. Therefore, the dispersion uniformity and the cohesiveness of the slurry can be improved, and the stress unevenness caused by the volume change of the subsequent material in the charging and discharging process is reduced. The additive comprises one or more of polyethylene glycol, sodium carboxymethylcellulose, sodium alginate, nonionic polyvinylpyrrolidone and polyacrylic acid. Thereby, the performance of the anode material obtained by the method can be further improved. Specifically, the weight ratio of silicon oxide, graphite, polyaniline and additives in the slurry is (5-15): (30-60): (5-11): (1-7). Thereby, the performance of the anode material obtained by the method can be further improved.
S200: calcining the precursor of the composite material to obtain the composite material
According to an embodiment of the invention, the composite precursor is subjected to a calcination treatment in this step to obtain a composite.
Specifically, the calcination treatment of the composite material precursor may be performed under an inert atmosphere. The temperature rise rate of the calcination treatment is 2-8 ℃/min, and the calcination treatment can comprise: keeping the temperature at 200-400 ℃ for 2-4 h, heating to a target temperature, keeping the temperature for 3-6 h, keeping the target temperature at 1100-1600 ℃, and then cooling to room temperature. Thereby, the performance of the anode material obtained by the method can be further improved. The calcination treatment by adopting the parameters is beneficial to forming a conductive framework with a framework more suitable for lithium ion insertion and extraction, the conductive polymer can connect graphite and form a loose framework structure, and SiO in the slurry is treatedxThe graphite and the conductive polymer are coated in the graphite and conductive polymer, so that the problem of volume expansion of the silicon-based material in the using process is better solved, and the graphite and the conductive polymer are calcined in the inert atmosphere to avoid the influence on the mechanical strength and the conductive performance of the framework structure due to excessive carbonization of the graphite and the conductive polymer.
According to the embodiment of the invention, after the calcination treatment, the operation of acid washing, washing and drying the composite material precursor subjected to the calcination treatment can be further included. Thereby, the performance of the anode material obtained by the method can be further improved.
Specifically, according to the embodiment of the invention, the solvent for acid cleaning is a mixed solution of hydrofluoric acid and hydrochloric acid, wherein the weight part of hydrofluoric acid is 90-99. Therefore, the effect of acid cleaning treatment can be further improved, and residual slurry impurities which are not completely attached to the conductive framework structure can be removed. According to the embodiment of the invention, the drying temperature is 60-150 ℃. Thereby, the performance of the anode material obtained by the method can be further improved.
S300: forming silicon particles using chemical vapor deposition
According to an embodiment of the invention, the silicon particles are formed in this step by chemical vapor deposition. Specifically, chemical vapor deposition includes: the composite material obtained in the previous step is used as a substrate, and silicon particles are formed on the surface, the inner part of pores and the polyaniline skeleton by deposition through a chemical vapor deposition method. Thereby, the performance of the anode material obtained by the method can be further improved.
According to an embodiment of the invention, the silicon particles formed have a particle size of less than 100 nm. Thereby, the performance of the anode material obtained by the method can be further improved. Specifically, the particle size of the formed silicon particles is moderate, and the nano silicon particles deposited by the CVD method can be better attached to a conductive framework formed by conductive polymers such as graphite, polyaniline and the like and are distributed more uniformly, so that the stability of a silicon-carbon interface is further enhanced, and the loose structure of the conductive framework is fully utilized to buffer the volume expansion of the silicon material. If the particle size of the silicon particles is too large, on one hand, the buffering effect of the conductive framework is weakened, and on the other hand, the silicon is easy to fall off in the using process, so that the service life of the cathode material is shortened.
According to a specific embodiment of the present invention, chemical vapor deposition comprises: injecting silane into a fluidized bed reactor at a temperature lower than the self-decomposition temperature of the silane, simultaneously injecting hydrogen and inert gas at a temperature higher than the temperature of the silane, mixing the gases, and enabling the temperature of the gas mixture to be close to the reaction temperature, wherein the reaction temperature is 500-700 ℃. Thereby, the performance of the anode material obtained by the method can be further improved. Thus, using silanesThe hydrogen-inert gas three-component vapor deposition process can relieve or even solve the defects of excessive dilution of reaction gas and higher reaction temperature required by the traditional silane pyrolysis process for preparing the nano silicon, and can form silicon particles with more proper particle size compared with a common chemical vapor deposition method. Therefore, on one hand, the process can be optimized, the production cost is reduced, namely, the process temperature, the energy consumption and the production cost are reduced, the process control difficulty is reduced, the method is suitable for industrial production, and on the other hand, better Si-SiO can be formedxA system of electrically conductive skeletons, and Si-SiOxCan be better embedded in the conductive framework.
According to the embodiment of the present invention, the specific type of the inert gas is not particularly limited, and for example, the inert gas may include a gas having functions of absorbing infrared light and improving thermal uniformity of the mixed gas, thereby further improving the reaction activity. Preferably, the inert gas may include He, Ne, N2And Ar. Thereby, the performance of the anode material obtained by the method can be further improved.
According to the embodiment of the invention, the gas mixture introduced into the fluidized bed reactor can be in a turbulent flow state, the residence time of the gas mixture is 5-66 s, and the total flow of the gas is 1-2 mol/s. Therefore, silicon particles with moderate particle size can be obtained, and the performance of the negative electrode material obtained by the method can be further improved.
According to the embodiment of the present invention, the gas partial pressure in the three-component reaction system is not particularly limited and may be adjusted by those skilled in the art according to the actual circumstances. For example, according to some specific embodiments of the present invention, the partial pressures of the three gases may be: 1-70 kPa silane, 93-990 kPa hydrogen, 1-1000 kPa inert gas and 100-2000 kPa total pressure. Thereby, the performance of the anode material obtained by the method can be further improved.
According to the embodiment of the invention, the molar fraction ratio of the silane in the silane-hydrogen subsystem is 0.01-0.1. Thereby, the performance of the anode material obtained by the method can be further improved.
According to the embodiment of the invention, the silicon loading amount in the material after chemical vapor deposition is 5-11 parts by weight. Thereby, the performance of the anode material obtained by the method can be further improved.
S400: performing carbon coating treatment to form the anode material
According to an embodiment of the present invention, a carbon coating treatment is performed in this step to form the foregoing anode material. Specifically, the carbon coating treatment may be carried out using a gas phase coating rotary kiln, and the air in the kiln is evacuated with nitrogen gas before coating so that the oxygen content in the kiln is less than 0.1 ppm. Thereby, the performance of the anode material obtained by the method can be further improved.
According to an embodiment of the present invention, the carbon source gas used for the cladding process includes one of methane, ethylene or acetylene, and the carrier gas includes one of nitrogen or argon; the coating temperature in the furnace is 500-1000 ℃, the flow rate of the carbon source gas is 90-130 ml/min, the rotating speed of the furnace body is 0.5-5 r/min, and the retention time of the materials in the furnace at high temperature is 50-120 min. Thereby, the performance of the anode material obtained by the method can be further improved.
According to the embodiment of the invention, the content of the coated carbon in the anode material subjected to the coating treatment is 7-18 parts by weight.
The carbon coating layer formed by the above process can more uniformly cover the Si-SiO formed previouslyxThe surface of the conductive framework can better improve the uniformity, integrity and strength of the formed amorphous carbon coating layer, reduce the contact of the material and electrolyte, improve the compatibility and facilitate the formation of a stable SEI film.
In another aspect of the invention, the invention provides an anode material for a lithium ion battery. The anode material includes: a skeletal structure comprising graphite and a conductive polymer; silicon oxide located at least one of inside and on a surface of the skeletal structure; silicon particles, wherein the silicon particles are positioned on the framework structure, and the particle size of the silicon particles is not more than 100 nm. The cathode material has at least one of the advantages of good cycle stability, high capacity retention rate, good conductivity and the like.
According to an embodiment of the present invention, the anode material is prepared using the method described above. Therefore, the negative electrode material has all the characteristics and advantages of the negative electrode material obtained by the method, and the description is omitted.
In yet another aspect of the present invention, a lithium ion battery is presented. Referring to fig. 2, the lithium ion battery includes: a positive electrode 100, a negative electrode 300, and a separator 200, the separator 200 separating the positive electrode 100 and the negative electrode 300, the negative electrode 300 including a negative electrode material, the negative electrode material being the aforementioned negative electrode material. Therefore, the lithium ion battery has all the characteristics and advantages of the cathode material obtained by the method, and the description is omitted.
It will be understood by those skilled in the art that the lithium ion battery may include, in addition to the foregoing negative electrode material, the necessary structures or components of a conventional lithium ion battery, such as positive electrode material, electrolyte, and case.
The invention will now be illustrated by means of specific examples, which are provided for illustration only and should not be construed as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications.
Example 1
Forming a composite material precursor slurry: SiO, graphite, polyaniline and an additive are mixed according to the weight ratio of 10: 50: 10: 8, mixing, wherein the graphite is spherical graphite with the median particle size of 20 microns, and the additive is polyethylene glycol. The rotational speed of sanding treatment is 1000r/min, sanding time is 6h, the solvent amount during sanding treatment is 60 parts by weight, drying treatment is air flow type spray drying, air inlet temperature is 180 ℃, air exhaust temperature is 80 ℃, slurry treatment amount is 6L/h, and then granulation is carried out.
And (3) calcining the granulated material, heating to 350 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 4 hours, heating to 1200 ℃, keeping the temperature for 5 hours, and then cooling to room temperature. And then carrying out acid pickling treatment in a mixed solution of hydrofluoric acid and hydrochloric acid, wherein the weight part of the hydrofluoric acid is 95, washing the mixed solution by deionized water until the washing solution is neutral, and drying the washed solution.
Silane is injected into a fluidized bed reactor at the temperature of 200 ℃, hydrogen and inert gas at the temperature of 300 ℃ are simultaneously injected, the gases are mixed, the temperature of the gas mixture is close to 600 ℃, the gas mixture in a turbulent flow state stays in the fluidized bed reactor for 30s, and the total flow rate of the gases is 1.5 mol/s.
Then, an amorphous carbon coating layer was formed by using a vapor phase coating rotary furnace, and the coated carbon content in the formed anode material was 15 parts by weight.
Example 2
The remaining parameters were the same as in example 1, except that polypyrrole was used as the conductive polymer.
Example 3
The remaining parameters were the same as in example 1, except that the gas mixture introduced into the fluidized-bed reactor during the deposition of the silicon particles was not in a turbulent state.
Example 4
The remaining parameters were the same as in example 1, except that no additives were added to the granulation slurry.
Example 5
The rest of the parameters were the same as example 1, except that silica was used as the silicon oxide in the granulation slurry.
Example 6
The remaining parameters were the same as in example 1, except that the chemical vapor deposition parameters for forming silicon particles were as follows:
silane, hydrogen and inert gas are introduced into a fluidized bed reactor after the temperature of a gas mixture is close to 600 ℃, a turbulent flow state is formed, the gas mixture in the turbulent flow state stays in the fluidized bed reactor for 5s, and the total flow rate of the gas is 1 mol/s.
Comparative example 1
The other parameters were the same as in example 1, except that silane and acetylene were used as gas sources and silicon particles were formed by deposition in a muffle furnace by chemical vapor deposition.
Comparative example 2
The remaining parameters were the same as in example 1, except that polyaniline was not added to the granulated slurry.
The negative electrode materials prepared in examples 1 to 6, and comparative examples 1 and 2 were slurried with a conductive agent and a binder and coated on the surface of a current collector to form a negative electrode, a positive electrode was a metal Li sheet, and the negative electrode and the positive electrode were spaced apart using a separator, and an electrolyte was a battery composed of lithium hexafluorophosphate (LiPF6) and a mixed solvent in an electrolyte, and first charge and discharge properties were tested, followed by a cycle rate test.
Examples 1-6 all had better cycle rate retention performance than comparative examples 1 and 2, with comparative example 1 having the most severe capacity drop after 200 cycles of the cycle test, example 1 having the best capacity retention, and examples 3, 5 and 6 having slightly lower performance than example 1, but all being better than comparative example 1. The cycle rate retention performance of comparative example 2 is slightly stronger than that of comparative example 1, but the first coulombic efficiency obtained by the first charge and discharge test is greatly reduced. In example 2, because polypyrrole is used, the first coulombic efficiency is lower than that in example 1, and the cycle rate retention performance is slightly lower than that in example 1, which may be caused by a decrease in performance of relieving volume expansion of silicon particles due to a difference in charge and discharge principles of polypyrrole from polyaniline and a decrease in pores of a skeleton structure formed by polypyrrole. Example 5, which used silica as the silicon oxide, resulted in slightly lower cycle rate retention performance than example 1, but still stronger than comparative examples 1 and 2.
The negative electrode materials formed in examples 3, 6 and 1 were tested by scanning electron microscopy, and the silicon particles in example 1 were all less than 100nm in size, with 70% of the particles being around 50-80nm in size. While the silicon particles formed in example 3 were larger in size, 70% of the particles were 80-150nm in size, the silicon particles formed in example 6 were lower in number, and a part of the particles were larger in size. Also, the rate retention performance after 200 cycles of the test in examples 3 and 6 is slightly lower than that in example 1, and the first coulombic efficiency in example 6 is also lower than that in example 1 because of less formed silicon particles.
In the description herein, references to the description of "one embodiment," "another embodiment," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A method of preparing an anode material for a lithium ion battery, comprising:
mixing silicon oxide, graphite and a conductive polymer to form slurry, and drying and granulating to obtain a composite material precursor;
calcining the composite material precursor to obtain a composite material;
depositing to form silicon particles on the conductive framework of the composite material by using chemical vapor deposition, wherein the chemical vapor deposition is realized in a fluidized bed reactor by adopting a silane-hydrogen-inert gas three-component reaction system;
and carrying out carbon coating treatment on the composite material with the silicon particles to form the negative electrode material.
2. The method of claim 1, wherein obtaining the composite precursor comprises: mixing the silicon oxide, graphite, conductive polymer and organic solvent, sanding, drying and granulating the sanded slurry, wherein the drying treatment comprises centrifugal or air-flow spray drying,
optionally, the graphite comprises one of natural graphite, artificial graphite, spheroidal graphite, preferably spheroidal graphite,
optionally, the particle size of the graphite is 5-20 μm;
optionally, the silicon oxide is SiOxWherein 0 is<x is less than or equal to 1, and the particle size of the silicon oxide is 0.1-0.2 mu m;
optionally, the organic solvent comprises one or more of absolute ethanol, acetone, benzene, N-methylpyrrolidone.
3. The method according to claim 2, wherein the rotation speed of the sanding treatment is 800-1200 r/min, the sanding time is 4-10 h, and the amount of the solvent used for the sanding treatment is 40-70 parts by weight;
the drying treatment is airflow type spray drying, the air inlet temperature of the drying treatment is 110-230 ℃, the air exhaust temperature is 70-90 ℃, and the slurry treatment capacity is 5-10L/h.
4. The method according to claim 2, wherein the slurry further comprises an additive, and the ratio of the silicon oxide, the graphite, the polyaniline and the additive in parts by weight is (5-15): (30-60): (5-11): (1-7);
optionally, the additive comprises one or more of polyethylene glycol, sodium carboxymethylcellulose, sodium alginate, nonionic polyvinylpyrrolidone and polyacrylic acid.
5. The method according to claim 1, wherein the calcination treatment of the composite material precursor is performed under an inert atmosphere, the temperature increase rate of the calcination treatment is 2-8 ℃/min,
the calcination treatment comprises: keeping the temperature at 200-400 ℃ for 2-4 h, heating to a target temperature, keeping the temperature for 3-6 h, wherein the target temperature is 1100-1600 ℃, and then cooling to room temperature;
optionally, after the calcination treatment, the composite material precursor subjected to the calcination treatment is further subjected to the operations of acid washing, washing and drying,
optionally, the pickling solvent is a mixed solution of hydrofluoric acid and hydrochloric acid, wherein the weight part of the hydrofluoric acid is 90-99;
optionally, the drying temperature is 60-150 ℃.
6. The method of claim 1, wherein the chemical vapor deposition comprises:
depositing the silicon particles on the surface, the inner part of the pores and the polyaniline skeleton of the graphite by using the composite material as a substrate and using a chemical vapor deposition method;
optionally, the silicon particles formed have a particle size of less than 100 nm;
optionally, the chemical vapor deposition comprises: injecting silane into a fluidized bed reactor at a temperature lower than the self-decomposition temperature of the silane, simultaneously injecting hydrogen and inert gas at a temperature higher than the temperature of the silane, mixing the gases, and enabling the temperature of the gas mixture to be close to the reaction temperature, wherein the reaction temperature is 500-700 ℃;
optionally, the inert gas comprises a gas having the functions of absorbing infrared light and improving the thermal uniformity of the mixed gas; preferably, the inert gas comprises He, Ne, N2At least one of Ar, Ar;
optionally, leading the gas mixture introduced into the fluidized bed reactor to be in a turbulent flow state, wherein the residence time of the gas mixture is 5-66 s, and the total flow of gas is 1-2 mol/s;
optionally, the partial pressures of gases in the three component reaction system are respectively: 1-70 kPa of silane, 93-990 kPa of hydrogen, 1-1000 kPa of inert gas and 100-2000 kPa of total pressure;
optionally, in the silane-hydrogen subsystem, the molar fraction of silane is 0.01-0.1;
optionally, the silicon loading in the material after the chemical vapor deposition is 5-11 parts by weight.
7. The method of claim 1, wherein the carbon coating treatment is carried out using a gas phase coating rotary furnace, and wherein the atmosphere in the furnace is evacuated with nitrogen gas before coating so that the oxygen content in the furnace is less than 0.1 ppm;
optionally, the carbon source gas used for the cladding process comprises one of methane, ethylene or acetylene, and the carrier gas comprises one of nitrogen or argon; the coating temperature in the furnace is 500-1000 ℃, the flow rate of the carbon source gas is 90-130 ml/min, the rotating speed of the furnace body is 0.5-5 r/min, the retention time of the materials in the furnace at high temperature is 50-120 min,
optionally, the content of the coated carbon in the anode material subjected to the coating treatment is 7-18 parts by weight.
8. An anode material for a lithium ion battery, comprising:
a skeletal structure comprising graphite and a conductive polymer;
silicon oxide located at least one of inside and on a surface of the skeletal structure;
silicon particles, wherein the silicon particles are positioned on the framework structure, and the particle size of the silicon particles is not more than 100 nm.
9. The negative electrode material of claim 8, wherein the negative electrode material is prepared by the method of any one of claims 1 to 7.
10. A lithium ion battery, comprising:
a positive electrode, a negative electrode, and a separator that separates the positive electrode and the negative electrode,
the negative electrode includes a negative electrode material as set forth in claim 8 or 9.
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