CN111653759A - Silicon-based composite material and preparation method thereof - Google Patents

Silicon-based composite material and preparation method thereof Download PDF

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Publication number
CN111653759A
CN111653759A CN202010542046.1A CN202010542046A CN111653759A CN 111653759 A CN111653759 A CN 111653759A CN 202010542046 A CN202010542046 A CN 202010542046A CN 111653759 A CN111653759 A CN 111653759A
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silicon
fast ion
ion conductor
coating agent
composite material
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查晓娟
刘兆平
季晶晶
王益
郎庆安
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Ningbo Fuli Battery Material Technology Co ltd
Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Fuli Battery Material Technology Co ltd
Ningbo Institute of Material Technology and Engineering of CAS
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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
    • H01M4/38—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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • 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
    • 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 silicon-based composite material and a preparation method thereof. The invention provides a silicon-based composite material, which comprises the following components: the silicon-based rapid ion conductor comprises a silicon-based substrate, a rapid ion conductor layer and a carbon layer, wherein the rapid ion conductor layer is coated on the surface of the silicon-based substrate; the fast ion conductor of the fast ion conductor layer is LiAlSixOyWherein x is more than or equal to 1, and y is more than or equal to 1. The invention sequentially coats a specific fast ion conductor layer LiAlSi on the surface of a silicon-based substratexOyThe problems of high charge transfer impedance and low power output of the silicon-based cathode material are effectively solved, and the multiplying power performance is improved; meanwhile, the specific double coating layers are matched, so that the expansion of the silicon-based material can be effectively relievedSwelling and improving the cycle performance.

Description

Silicon-based composite material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a silicon-based composite material and a preparation method thereof.
Background
Over the past 20 years, lithium ion batteries have dominated the portable electronic device market and have made tremendous progress in the electric vehicle industry. Graphite is used as a negative electrode material most used by lithium ion batteries, the theoretical capacity of the graphite is 372mAh/g, the energy density is below 150Wh/kg, and the requirement of 350Wh/kg of energy density is far from being met, so that the research on novel negative electrode materials of the lithium ion batteries is urgent.
The silicon negative electrode material is considered to be most hopeful to replace graphite due to the fact that the theoretical capacity is up to 3590mAh/g, the working platform voltage is high, the environment is friendly, and the reserves are abundant, and the silicon negative electrode material is expected to occupy the main position in the market of the negative electrode material in the future. However, in the practical use process of the silicon negative electrode, there are also many challenges, and in the charge and discharge process of the silicon negative electrode, the volume expansion reaches up to 300%, which causes pulverization of the silicon material and cracking and regeneration of the SEI film, so that the capacity of the silicon negative electrode material is rapidly reduced, the first coulombic efficiency is low, and meanwhile, in the aspect of market application, there are also higher requirements for the quick charge and quick discharge performance.
To solve the above problems, a large number of researchers improve the swelling and improve the cycle stability and rate capability of the material by various methods. The main technical means include two types: firstly, directly carry out structural design to the silicon material, include: solid structure designs such as thin films, nanowires and nanorods and hollow structure designs such as nanotubes, hollow spheres and porous silicon; and secondly, introducing other functional materials to be compounded with the silicon-based materials, and comprehensively optimizing the structural design, such as metal material modification, conductive carbon material modification, complex structural design optimization and the like. For example, in CN108682796A, an alloy is used as a coating layer, in CN108493428A, a fast ion lithium salt is used as a coating layer, and in CN109950481A, a polymer electrolyte is used as a coating layer. However, the above coating materials still cannot effectively improve the cycle stability and rate capability, and the preparation method has the disadvantages of complicated process, low coating layer strength, uneven coating thickness and the like.
Disclosure of Invention
In view of the above, the present invention provides a silicon-based composite material and a method for preparing the same. The silicon-based composite material provided by the invention can effectively improve the cycle stability and the rate capability. The preparation method provided by the invention is simple and feasible and has a good coating effect.
The invention provides a silicon-based composite material, which comprises the following components:
a silicon-based matrix, a silicon-based substrate,
a fast ion conductor layer coated on the surface of the silicon-based substrate,
and a carbon layer coated on the surface of the fast ion conductor layer;
the fast ion conductor of the fast ion conductor layer is LiAlSixOyWherein x is more than or equal to 1, and y is more than or equal to 1.
Preferably, the silicon-based matrix is SiOzWherein z is more than or equal to 0.6 and less than or equal to 1.6.
Preferably, the fast ion conductor is selected from LiAlSiO4、LiAlSi2O6And LiAlSi3O8One or more of them.
Preferably, the mass ratio of the silicon-based matrix to the fast ion conductor layer is 1: 0.01-10;
the mass ratio of the silicon-based matrix to the carbon layer is 1: 0.001-0.5.
The invention also provides a preparation method of the silicon-based composite material in the technical scheme, which comprises the following steps:
a) dissolving an aluminum salt compound, a lithium salt compound and silicon dioxide in a solvent and then sintering to obtain a fast ion coating agent;
b) mixing a silicon-based matrix with the fast ion coating agent to obtain precursor powder;
c) and mixing the precursor powder, a carbon source and a liquid phase coating agent, and sintering to obtain the silicon-based composite material.
Preferably, the aluminum salt compound is selected from one or more of aluminum isopropoxide, aluminum sec-butoxide, aluminum sulfate and aluminum nitrate;
the lithium salt compound is selected from one or more of lithium carbonate, lithium hydroxide, lithium acetate and lithium citrate.
Preferably, the D50 particle size of the silicon-based matrix is 2-10 μm.
Preferably, in the step a), the mass ratio of the aluminum salt compound to the lithium salt compound to the silicon dioxide is 1: 0.5-1: 1.5-3;
in the step c), the mass ratio of the precursor powder, the carbon source and the liquid phase coating agent is (80-100) to (0-10).
Preferably, in the step a), the sintering temperature is 850-1200 ℃, and the heat preservation time is 3-5 h.
In the step c), the sintering temperature is 500-850 ℃, and the heat preservation time is 3-5 h.
Preferably, in step c):
the carbon source is selected from one or more of asphalt, glucose, sucrose and chitosan;
the liquid phase coating agent is selected from one or more of heavy oil, liquid phenolic resin and liquid epoxy resin;
in the step a), the solvent is an alcohol solvent.
The invention provides a silicon-based composite material, which comprises the following components: the silicon-based rapid ion conductor comprises a silicon-based substrate, a rapid ion conductor layer and a carbon layer, wherein the rapid ion conductor layer is coated on the surface of the silicon-based substrate; the fast ion conductor of the fast ion conductor layer is LiAlSixOyWherein x is more than or equal to 1, and y is more than or equal to 1. The invention sequentially coats a specific fast ion conductor layer LiAlSi on the surface of a silicon-based substratexOyThe problems of high charge transfer impedance and low power output of the silicon-based cathode material are effectively solved, and the multiplying power performance is improved; meanwhile, the specific double coating layers are matched, so that the expansion of the silicon-based material can be effectively relieved, and the cycle performance is improved.
Test results show that the 0.2C initial discharge specific capacity of the silicon-based composite material provided by the invention serving as a lithium ion battery cathode material reaches 1609 mAh.g-1Above, the first efficiency reaches more than 80%, and the discharge capacity is maintained at 1C, 2C and 3C multiplying powerThe rate reaches more than 93 percent, more than 92 percent and more than 84 percent respectively, and the specific discharge capacity can still be kept at 1284mAh g after 0.2C circulation for 200 times-1Above, the capacity retention rate reaches 79% or more.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an XRD pattern of the fast ion capping agent of example 1;
FIG. 2 is an SEM photograph of the composite material obtained in example 1;
FIG. 3 is a graph showing cycle characteristics of the composite material obtained in example 1 as a negative electrode material.
Detailed Description
The invention provides a silicon-based composite material, which comprises the following components:
a silicon-based matrix, a silicon-based substrate,
a fast ion conductor layer coated on the surface of the silicon-based substrate,
and a carbon layer coated on the surface of the fast ion conductor layer;
the fast ion conductor of the fast ion conductor layer is LiAlSixOyWherein x is more than or equal to 1, and y is more than or equal to 1.
The invention sequentially coats a specific fast ion conductor layer LiAlSi on the surface of a silicon-based substratexOyThe problems of high charge transfer impedance and low power output of the silicon-based cathode material are effectively solved, and the multiplying power performance is improved; meanwhile, the specific double coating layers are matched, so that the expansion of the silicon-based material can be effectively relieved, and the cycle performance is improved.
In the invention, the silicon-based substrate is preferably a silica material SiOzWherein z is more than or equal to 0.6 and less than or equal to 1.6. Compared with other silicon-based materials (such as nano silicon and the like), the silicon oxide material is adopted in the inventionSiOzThe rate capability and cycle performance can be improved more effectively by the coating. In some embodiments of the invention, the silicon-based substrate is SiOzAnd z is 0.9.
In the invention, the particle size D50 of the silicon-based matrix is preferably 2-10 μm, and more preferably 3-5 μm. If the particle size is too high, the electrochemical performance of the composite material is rapidly degraded in the charging and discharging process, and the use requirement cannot be met, and if the particle size is too small, the dispersion is not facilitated, the preparation is difficult, and the composite material with good performance is difficult to obtain.
In the invention, the fast ion conductor of the fast ion conductor layer is LiAlSixOyWherein x is more than or equal to 1, and preferably 1-3; y is more than or equal to 1, preferably 4-8. Compared with other fast ion conductors, the fast ion conductor can better match with a carbon layer, has obvious improvement effect on a silicon substrate, and improves the rate capability and the cycle performance of the material. The fast ion conductor is more preferably LiAlSiO4、LiAlSi2O6And LiAlSi3O8One or more of them.
In the present invention, the carbon layer is preferably an amorphous carbon layer.
In the present invention, the composite material comprises three layers: a silicon-based substrate core layer, a fast ion conductor intermediate layer and a carbon outer layer. The mass ratio of the silicon-based matrix to the fast ion conductor layer is preferably 1 to (0.01-0.5); in some embodiments of the invention, the mass ratio is 1: 0.03, 1: 0.05, or 1: 0.1. The mass ratio of the silicon-based matrix to the carbon layer is preferably 1 to (0.001-0.5). In the invention, the particle size of the composite material is preferably 3-5 μm.
The invention also provides a preparation method of the silicon-based composite material in the technical scheme, which comprises the following steps:
a) dissolving an aluminum salt compound, a lithium salt compound and silicon dioxide in a solvent and then sintering to obtain a fast ion coating agent;
b) mixing a silicon-based matrix with the fast ion coating agent to obtain precursor powder;
c) and mixing the precursor powder, a carbon source and a liquid phase coating agent, and sintering to obtain the silicon-based composite material.
With respect to step a):
in the present invention, the aluminum salt compound is preferably one or more of aluminum isopropoxide, aluminum sec-butoxide, aluminum sulfate and aluminum nitrate. The lithium salt compound is preferably one or more of lithium carbonate, lithium hydroxide, lithium acetate and lithium citrate. The particle size of the silicon dioxide is preferably 0.5-2 μm, and more preferably 1-1.2 μm. In the invention, the mass ratio of the aluminum salt compound, the lithium salt compound and the silicon dioxide is preferably 1 to (0.5-1) to (1.5-3); in some embodiments of the invention, the mass ratio is 1: 0.5: 1.5 or 1: 3.
In the invention, the solvent is preferably an alcohol solvent, and more preferably one or more of ethanol, n-propanol, isopropanol, ethylene glycol and glycerol.
In the present invention, the mass fraction of the total solid raw materials (aluminum salt compound, lithium salt compound, and silica) in the solvent is preferably 10% to 90%. Dissolving and dispersing the solid raw materials in a solvent uniformly to obtain a mixed solution.
In the present invention, stirring is preferably accompanied in the process of mixing the solid raw material with the solvent; the stirring speed is preferably 100-400 r/min, and the stirring time is preferably 1-6 h; for better dispersion, the stirring time is more preferably 6 h. After the above treatment, the solid raw material is uniformly dispersed in the solvent.
In the present invention, it is preferable to further dry the mixture after the mixing. The drying temperature is preferably 60-120 ℃, and the drying time is preferably 3-8 h.
In the present invention, it is preferable to further perform grinding after the above-mentioned drying. After the above drying, the granules are adhered together into a sheet or a block, and the granules are dispersed by grinding to obtain uniformly dispersed granules without changing the particle size of the granules themselves.
In the present invention, after grinding, sintering is performed. In the present invention, the sintering is preferably performed in an inert gas atmosphere; the inert gas used in the present invention is not particularly limited, and may be any of conventional inert gases known to those skilled in the art, such as argonQi, etc. In the invention, the sintering temperature is preferably 850-1200 ℃; in some embodiments of the invention, the sintering temperature is 1000 ℃. The heat preservation time is preferably 3-5 h; in some embodiments of the invention, the incubation time is 5 hours. The heating rate in the sintering is preferably 4-8 ℃/min; in some embodiments of the invention, the ramp rate is 5 deg.C/min. After sintering, the raw materials react to form the fast ion conductor coating agent LiAlSixOyWherein x is more than or equal to 1, and y is more than or equal to 1.
With respect to step b):
in the present invention, the silicon-based matrix material is the same as that described in the above technical solution, and is not described herein again. In the invention, the mass ratio of the silicon-based matrix to the fast ion coating agent is preferably 1 to (0.001-0.5); in some embodiments of the invention, the mass ratio is 1: 0.03, 1: 0.05, or 1: 0.1.
In the present invention, the mixing is preferably ball milling. The rotation speed of the ball milling is preferably 200-500 r/min, and more preferably 400 r/min; the ball milling time is preferably 0.5-4 h, and more preferably 2 h. And performing ball milling and mixing to obtain precursor powder.
With respect to step c):
in the invention, the carbon source is preferably one or more of asphalt, glucose, sucrose and chitosan. The liquid phase coating agent is preferably one or more of heavy oil, liquid phenolic resin and liquid epoxy resin.
In the invention, the mass ratio of the precursor powder, the carbon source and the liquid phase coating agent is preferably (80-100) to (0-10), wherein the mass ratio of the carbon source and the liquid phase coating agent is not 0. In some embodiments of the invention, the mass ratio is 90: 5.
In the present invention, the mixing temperature of the precursor powder, the carbon source, and the liquid phase coating agent is not particularly limited, and may be normal temperature. In the invention, the mixing equipment can be a fusion machine, a VC mixer or a ball mill. The rotation speed in the mixing process is preferably 100-400 r/min, and the mixing time is preferably 30-300 min.
In the invention, after being uniformly mixed, the mixture is sintered. In the present invention, the sintering is preferably performed in an inert gas atmosphere; the inert gas used in the present invention is not particularly limited, and may be any conventional inert gas known to those skilled in the art, such as argon. In the invention, the sintering temperature is preferably 500-850 ℃; in some embodiments of the invention, the sintering temperature is 650 ℃. The heat preservation time is preferably 3-5 h; in some embodiments of the invention, the incubation time is 5 hours. The heating rate in the sintering is preferably 4-8 ℃/min; in some embodiments of the invention, the ramp rate is 5 deg.C/min. After sintering, the surface of the silicon-based substrate is tightly coated with the aluminum silicate fast ion conductor layer, and a carbon coating layer is formed on the surface of the aluminum silicate coating layer, so that the silicon-based composite material with a three-layer structure is obtained.
The preparation method provided by the invention is simple and easy to implement, and uniform in coating, and the coating effect is improved.
The invention has the following beneficial effects:
(1) designing a double-coating layer on the surface of a silicon-based substrate, and sequentially forming a fast ion conductor layer LiAlSixOyAnd a carbon layer. The coated composite material is used as the negative electrode material of the lithium ion battery, and the 0.2C first discharge specific capacity of the composite material reaches 1609 mAh.g-1Above, the first efficiency reaches more than 80%, the discharge capacity retention rates at 1C, 2C and 3C multiplying powers reach more than 93%, more than 92% and more than 84%, respectively, and the discharge specific capacity can still be maintained at 1284mAh g after 0.2C circulation for 200 times-1Therefore, the lithium ion battery anode material has great potential as a lithium ion battery anode material.
(2) The invention utilizes aluminum-containing compound, lithium-containing compound and silicon dioxide powder to synthesize fast ion conductor lithium aluminum silicate as a coating substance, the chemical synthesis method uniformly coats the surface of a silicon-based matrix, and the novel silicon-based negative electrode material with a coating layer tightly contacted with the material is formed after firing.
(3) The lithium aluminum silicate is used as an excellent coating substance for conducting lithium ions, and a precursor of the lithium aluminum silicate forms a coating layer with good crystallinity after being fired, so that the lithium ions can be conveniently de-embedded in the material, the rate capability of the material is improved, and meanwhile, the lithium aluminum silicate is used as the coating layer, so that the volume expansion is relieved to a certain extent, and the lithium aluminum silicate is matched with a carbon layer, so that the expansion problem is well improved, and the cycle performance of the material is improved.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims. The experimental methods described in the following examples, as specifically indicated, are all conventional methods; the reagents and materials used, unless otherwise indicated, are commercially available. Wherein, SiO2The particle size of the powder is 0.5 to 2 μm.
Example 1
S1, weighing 20g of aluminum sec-butoxide, 10g of lithium carbonate and SiO230g of the powder was dissolved in 50mL of an ethanol solution, stirred with a magnetic stirrer for 4 hours, and after stirring uniformly, dried at 80 ℃ for 5 hours, and then the dried product was ground to obtain a mixture A. And sintering in argon atmosphere at the heating rate of 5 ℃/min, heating to 1000 ℃, and keeping the temperature for 5h to obtain the fast ion coating agent.
S2 weighing SiO 2z(z is 0.9, the granularity is 3 mu m)200g and fast ion coating agent 10g are put into a ball milling tank for ball milling at the rotating speed of 400r/min for 2h to obtain precursor powder.
S3, adding the precursor powder, the asphalt and the liquid phenolic resin into a fusion machine according to the mass ratio of 90: 5, stirring at normal temperature at the rotating speed of 300r/min, and mixing for 30min to obtain a mixture.
S4, placing the mixture into a crucible, sintering in an argon atmosphere, heating to 650 ℃ at a heating speed of 5 ℃/min, and keeping the temperature for 5h to obtain the composite material.
The fast ion coating agent obtained in step S1 is subjected to an X-ray diffraction test, and the result is shown in fig. 1, where fig. 1 is an XRD pattern of the fast ion coating agent in example 1 of the present invention. The obtained fast ion coating agent is proved to be LiAlSi3O8。
Scanning electron microscope characterization is performed on the composite material obtained in step S4, and the result is shown in fig. 2, and fig. 2 is an SEM image of the composite material obtained in example 1. As can be seen, the particle size of the obtained composite material is 3-5 μm; the coating layer on the surface of the particle is uniform.
Example 2
S1, weighing 20g of aluminum sec-butoxide, 10g of lithium carbonate and SiO230g of the powder was dissolved in 50mL of an ethanol solution, stirred with a magnetic stirrer for 4 hours, and after stirring uniformly, dried at 80 ℃ for 5 hours, and then the dried product was ground to obtain a mixture A. And sintering in argon atmosphere at the heating rate of 5 ℃/min, heating to 1000 ℃, and keeping the temperature for 5h to obtain the fast ion coating agent.
S2 weighing SiO 2z(z is 0.9, the granularity is 3 mu m)100g and fast ion coating agent 10g are put into a ball milling tank for ball milling at the rotating speed of 400r/min for 2h to obtain precursor powder.
S3, adding the precursor powder, the asphalt and the liquid phenolic resin into a fusion machine according to the mass ratio of 90: 5, stirring at normal temperature at the rotating speed of 300r/min, and mixing for 30min to obtain a mixture.
S4, placing the mixture into a crucible, sintering in an argon atmosphere, heating to 650 ℃ at a heating speed of 5 ℃/min, and keeping the temperature for 5h to obtain the composite material.
The X-ray diffraction test of the fast ion coating agent obtained in the step S1 was carried out according to the analytical test method of example 1, and the result showed that the fast ion coating agent obtained was LiAlSi3O8。
Example 3
S1, weighing 20g of aluminum sec-butoxide, 10g of lithium carbonate and SiO230g of the powder was dissolved in 50mL of an ethanol solution, stirred with a magnetic stirrer for 4 hours, and after stirring uniformly, dried at 80 ℃ for 5 hours, and then the dried product was ground to obtain a mixture A. And sintering in argon atmosphere at the heating rate of 5 ℃/min, heating to 1000 ℃, and keeping the temperature for 5h to obtain the fast ion coating agent.
S2 weighing SiO 2z(z is 0.9, the particle size is 3 mu m)300g and fast ion coating agent 10g are put into a ball milling tank for ball milling, and the rotating speed is 400r/miAnd n, performing ball milling for 2h to obtain precursor powder.
S3, adding the precursor powder, the asphalt and the liquid phenolic resin into a fusion machine according to the mass ratio of 90: 5, stirring at normal temperature at the rotating speed of 300r/min, and mixing for 30min to obtain a mixture.
S4, placing the mixture into a crucible, sintering in an argon atmosphere, heating to 650 ℃ at a heating speed of 5 ℃/min, and keeping the temperature for 5h to obtain the composite material.
The X-ray diffraction test of the fast ion coating agent obtained in the step S1 was carried out according to the analytical test method of example 1, and the result showed that the fast ion coating agent obtained was LiAlSi3O8。
Example 4
S1, weighing 10g of aluminum sec-butoxide, 10g of lithium carbonate and SiO230g of the powder was dissolved in 50mL of an ethanol solution, stirred with a magnetic stirrer for 4 hours, and after stirring uniformly, dried at 80 ℃ for 5 hours, and then the dried product was ground to obtain a mixture A. And sintering in argon atmosphere at the heating rate of 5 ℃/min, heating to 1000 ℃, and keeping the temperature for 5h to obtain the fast ion coating agent.
S2 weighing SiO 2z(z is 0.9, the granularity is 3 mu m)200g and fast ion coating agent 10g are put into a ball milling tank for ball milling at the rotating speed of 400r/min for 2h to obtain precursor powder.
S3, adding the precursor powder, the asphalt and the liquid phenolic resin into a fusion machine according to the mass ratio of 90: 5, stirring at normal temperature at the rotating speed of 300r/min, and mixing for 30min to obtain a mixture.
S4, placing the mixture into a crucible, sintering in an argon atmosphere, heating to 650 ℃ at a heating speed of 5 ℃/min, and keeping the temperature for 5h to obtain the composite material.
The X-ray diffraction test of the fast ion coating agent obtained in the step S1 was carried out according to the analytical test method of example 1, and the result showed that the fast ion coating agent obtained was LiAlSi3O8Containing a small amount of impurity LiSi3O6。
Example 5
S1, weighing 20g of aluminum sec-butoxide, 10g of lithium citrate and SiO230g of powder is dissolvedAfter stirring with a magnetic stirrer for 4 hours in 50mL of an ethanol solution and stirring uniformly, the mixture was dried at 80 ℃ for 5 hours, and then the dried product was ground to obtain a mixture A. And sintering in argon atmosphere at the heating rate of 5 ℃/min, heating to 1000 ℃, and keeping the temperature for 5h to obtain the fast ion coating agent.
S2 weighing SiO 2z(z is 0.9, the granularity is 3 mu m)300g and fast ion coating agent 10g are put into a ball milling tank for ball milling at the rotating speed of 400r/min for 2h to obtain precursor powder.
S3, adding the precursor powder, the asphalt and the liquid phenolic resin into a fusion machine according to the mass ratio of 90: 5, stirring at normal temperature at the rotating speed of 300r/min, and mixing for 30min to obtain a mixture.
S4, placing the mixture into a crucible, sintering in an argon atmosphere, heating to 650 ℃ at a heating speed of 5 ℃/min, and keeping the temperature for 5h to obtain the composite material.
The X-ray diffraction test of the fast ion coating agent obtained in the step S1 was carried out according to the analytical test method of example 1, and the result showed that the fast ion coating agent obtained was LiAlSi3O8。
Example 6
S1, weighing 20g of aluminum sulfate, 10g of lithium citrate and SiO230g of the powder was dissolved in 50mL of an ethanol solution, stirred with a magnetic stirrer for 4 hours, and after stirring uniformly, dried at 80 ℃ for 5 hours, and then the dried product was ground to obtain a mixture A. And sintering in argon atmosphere at the heating rate of 5 ℃/min, heating to 1000 ℃, and keeping the temperature for 5h to obtain the fast ion coating agent.
S2 weighing SiO 2z(z is 0.9, the granularity is 3 mu m)300g and fast ion coating agent 10g are put into a ball milling tank for ball milling at the rotating speed of 400r/min for 2h to obtain precursor powder.
S3, adding the precursor powder, the asphalt and the liquid phenolic resin into a fusion machine according to the mass ratio of 90: 5, stirring at normal temperature at the rotating speed of 300r/min, and mixing for 30min to obtain a mixture.
S4, placing the mixture into a crucible, sintering in an argon atmosphere, heating to 650 ℃ at a heating speed of 5 ℃/min, and keeping the temperature for 5h to obtain the composite material.
The X-ray diffraction test of the fast ion coating agent obtained in the step S1 was carried out according to the analytical test method of example 1, and the result showed that the fast ion coating agent obtained was LiAlSi3O8。
Example 7
S1, weighing 20g of aluminum sec-butoxide, 10g of lithium carbonate and SiO230g of the powder was dissolved in 50mL of an ethanol solution, stirred with a magnetic stirrer for 4 hours, and after stirring uniformly, dried at 80 ℃ for 5 hours, and then the dried product was ground to obtain a mixture A. And sintering in argon atmosphere at the heating rate of 5 ℃/min, heating to 1000 ℃, and keeping the temperature for 5h to obtain the fast ion coating agent.
S2 weighing SiO 2z(z is 0.9, the particle size is 4 mu m)200g and fast ion coating agent 10g, and the mixture is put into a ball milling tank for ball milling at the rotating speed of 400r/min for 2h to obtain precursor powder.
S3, adding the precursor powder, the asphalt and the liquid phenolic resin into a fusion machine according to the mass ratio of 90: 5, stirring at normal temperature at the rotating speed of 300r/min, and mixing for 30min to obtain a mixture.
S4, placing the mixture into a crucible, sintering in an argon atmosphere, heating to 650 ℃ at a heating speed of 5 ℃/min, and keeping the temperature for 5h to obtain the composite material.
The X-ray diffraction test of the fast ion coating agent obtained in the step S1 was carried out according to the analytical test method of example 1, and the result showed that the fast ion coating agent obtained was LiAlSi3O8。
Example 8
S1, weighing 20g of aluminum sec-butoxide, 10g of lithium carbonate and SiO230g of the powder was dissolved in 50mL of an ethanol solution, stirred with a magnetic stirrer for 4 hours, and after stirring uniformly, dried at 80 ℃ for 5 hours, and then the dried product was ground to obtain a mixture A. And sintering in argon atmosphere at the heating rate of 5 ℃/min, heating to 1000 ℃, and keeping the temperature for 5h to obtain the fast ion coating agent.
S2 weighing SiO 2z(z is 0.9, the granularity is 5 mu m)200g and fast ion coating agent 10g are put into a ball milling tank for ball milling at the rotating speed of 400r/min for 2h,obtaining precursor powder.
S3, adding the precursor powder, the asphalt and the liquid phenolic resin into a fusion machine according to the mass ratio of 90: 5, stirring at normal temperature at the rotating speed of 300r/min, and mixing for 30min to obtain a mixture.
S4, placing the mixture into a crucible, sintering in an argon atmosphere, heating to 650 ℃ at a heating speed of 5 ℃/min, and keeping the temperature for 5h to obtain the composite material.
The X-ray diffraction test of the fast ion coating agent obtained in the step S1 was carried out according to the analytical test method of example 1, and the result showed that the fast ion coating agent obtained was LiAlSi3O8。
Comparative example 1
S1, weighing 10g of lithium carbonate and SiO230g of the powder was dissolved in 50mL of an ethanol solution, stirred with a magnetic stirrer for 4 hours, and after stirring uniformly, dried at 80 ℃ for 5 hours, and then the dried product was ground to obtain a mixture A. And sintering in argon atmosphere at the heating rate of 5 ℃/min, heating to 1000 ℃, and keeping the temperature for 5h to obtain the fast ion coating agent.
S2 weighing SiO 2z(z is 0.9, the granularity is 3 mu m)200g and fast ion coating agent 10g are put into a ball milling tank for ball milling at the rotating speed of 400r/min for 2h to obtain precursor powder.
S3, adding the precursor powder, the asphalt and the liquid phenolic resin into a fusion machine according to the mass ratio of 90: 5, stirring at normal temperature at the rotating speed of 300r/min, and mixing for 30min to obtain a mixture.
S4, placing the mixture into a crucible, sintering in an argon atmosphere, heating to 650 ℃ at a heating speed of 5 ℃/min, and keeping the temperature for 5h to obtain the composite material.
The X-ray diffraction test of the fast ion coating agent obtained in the step S1 was carried out according to the analytical test method of example 1, and the result showed that the fast ion coating agent obtained was LiSi3O6Since no aluminum salt is added to the raw material, a lithium aluminum silicate fast ion conductor cannot be formed.
Comparative example 2
S1, weighing 20g of aluminum sec-butoxide and SiO230g of powder, dissolved in 50mL of ethanol solutionStirring with a magnetic stirrer for 4h, stirring well, drying at 80 deg.C for 5h, and grinding the dried product to obtain mixture A. And sintering in argon atmosphere at the heating rate of 5 ℃/min, and heating to 1000 ℃ for 5h to obtain the coating agent.
S2 weighing SiO 2z(z is 0.9, the granularity is 3 mu m)200g and 10g of coating agent are put into a ball milling tank for ball milling at the rotating speed of 400r/min for 2h to obtain precursor powder.
S3, adding the precursor powder, the asphalt and the liquid phenolic resin into a fusion machine according to the mass ratio of 90: 5, stirring at normal temperature at the rotating speed of 300r/min, and mixing for 30min to obtain a mixture.
S4, placing the mixture into a crucible, sintering in an argon atmosphere, heating to 650 ℃ at a heating speed of 5 ℃/min, and keeping the temperature for 5h to obtain the composite material.
The X-ray diffraction test of the coating agent obtained in step S1 was carried out in accordance with the analytical test method of example 1, and it was revealed that the coating agent obtained was Al2O3And SiO2(ii) a Because the raw materials do not contain lithium salt, fast ion conductors, aluminum salt and SiO cannot be generated2Has no effect.
Example 9
The electrochemical performance test of the silicon-based composite materials obtained in the above examples and comparative examples is carried out by the following processes:
mixing and pulping the obtained silicon-based composite negative electrode material, conductive carbon black, CMC, SBR and deionized water solvent according to the mass ratio of 53: 24: 7: 16: 90, wherein the pulping time is 12 hours. Uniformly coating the prepared slurry on a copper foil (the coating thickness is 20mm), and carrying out forced air drying at 80 ℃ for 12 h; and cutting and rolling to obtain the negative plate. The lithium sheet is taken as a counter electrode, and the electrolyte is LiPF6The solution (the mass fraction of the solution is 35%, the solvent is DMC, EMC and EC, the volume ratio of the DMC, the EMC and the EC is 1: 1) and the diaphragm is a polyethylene microporous membrane 2400, a button type simulated battery is assembled, and the electrochemical performance test is carried out after the button type simulated battery is kept stand for 5 hours.
And (3) carrying out charge and discharge performance test by adopting a blue battery system, wherein the test current density is 0.1C/g and 0.2C/g, and the charge and discharge test is carried out within the voltage range of 0.005-2V.
The test results are shown in Table 1.
TABLE 1 electrochemical Properties of examples and comparative examples
Figure BDA0002539243890000121
The cycle performance curve of the silicon-based composite anode material of example 1 at 0.2C is shown in fig. 3, and fig. 3 is a cycle performance curve graph of the composite material obtained in example 1 as an anode material.
The test results in table 1 show that, compared with the comparative example, the first specific discharge capacity, the capacity retention rate under different multiplying powers and the first coulombic efficiency of the material obtained in the embodiment of the present invention are all significantly improved, and meanwhile, the capacity and the capacity retention rate after 200 cycles are also significantly improved, which proves that the material provided by the present invention can effectively improve the multiplying power performance and the cycling stability.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A silicon-based composite, comprising:
a silicon-based matrix, a silicon-based substrate,
a fast ion conductor layer coated on the surface of the silicon-based substrate,
and a carbon layer coated on the surface of the fast ion conductor layer;
the fast ion conductor of the fast ion conductor layer is LiAlSixOyWherein x is more than or equal to 1, and y is more than or equal to 1.
2. The composite material according to claim 1,the silicon-based matrix is SiOzWherein z is more than or equal to 0.6 and less than or equal to 1.6.
3. The composite material of claim 1, wherein the fast ion conductor is selected from the group consisting of LiAlSiO4、LiAlSi2O6And LiAlSi3O8One or more of them.
4. The composite material of claim 1, wherein the mass ratio of the silicon-based matrix to the fast ion conductor layer is 1: 0.01-10;
the mass ratio of the silicon-based matrix to the carbon layer is 1: 0.001-0.5.
5. A preparation method of the silicon-based composite material as defined in any one of claims 1-4, comprising the following steps:
a) dissolving an aluminum salt compound, a lithium salt compound and silicon dioxide in a solvent and then sintering to obtain a fast ion coating agent;
b) mixing a silicon-based matrix with the fast ion coating agent to obtain precursor powder;
c) and mixing the precursor powder, a carbon source and a liquid phase coating agent, and sintering to obtain the silicon-based composite material.
6. The preparation method according to claim 5, wherein the aluminum salt compound is selected from one or more of aluminum isopropoxide, aluminum sec-butoxide, aluminum sulfate and aluminum nitrate;
the lithium salt compound is selected from one or more of lithium carbonate, lithium hydroxide, lithium acetate and lithium citrate.
7. The preparation method according to claim 5, wherein the silicon-based matrix has a D50 particle size of 2-10 μm.
8. The preparation method according to claim 5, wherein in the step a), the mass ratio of the aluminum salt compound to the lithium salt compound to the silicon dioxide is 1: 0.5-1: 1.5-3;
in the step c), the mass ratio of the precursor powder, the carbon source and the liquid phase coating agent is (80-100) to (0-10).
9. The preparation method of claim 5, wherein in the step a), the sintering temperature is 850-1200 ℃ and the holding time is 3-5 h.
In the step c), the sintering temperature is 500-850 ℃, and the heat preservation time is 3-5 h.
10. The method of claim 5, wherein in step c):
the carbon source is selected from one or more of asphalt, glucose, sucrose and chitosan;
the liquid phase coating agent is selected from one or more of heavy oil, liquid phenolic resin and liquid epoxy resin;
in the step a), the solvent is an alcohol solvent.
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