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CN114804116B - Modification preparation method of silicon oxide negative electrode material of lithium ion battery - Google Patents

Modification preparation method of silicon oxide negative electrode material of lithium ion battery Download PDF

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CN114804116B
CN114804116B CN202110116216.4A CN202110116216A CN114804116B CN 114804116 B CN114804116 B CN 114804116B CN 202110116216 A CN202110116216 A CN 202110116216A CN 114804116 B CN114804116 B CN 114804116B
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lithium
silicon oxide
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ion battery
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CN114804116A (en
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崔光磊
管芃
许高洁
谢斌
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

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  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention belongs to the field of lithium ion battery materials, and particularly relates to a modified preparation method of a high-first-effect silicon oxide negative electrode material used as a negative electrode material of a lithium ion battery. According to the invention, pure silicon oxide (SiO) and lithium salt are ball-milled according to a certain proportion, then are calcined in inert atmosphere, lithium-containing interface components are generated by calcining the lithium salt, and lithium is supplemented to the material by adjusting the interface composition of the material. Therefore, lithium ion loss in the circulation process can be effectively supplemented, so that the material has higher initial coulomb efficiency, higher specific capacity and circulation stability. The synthesis process has high production efficiency, simple process and low cost, can be applied to large-scale industrial production, and can be widely applied to the fields of electronic products, electric automobiles and the like.

Description

Modification preparation method of silicon oxide negative electrode material of lithium ion battery
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a modified preparation method of a high-first-effect silicon oxide negative electrode material used as a negative electrode material of a lithium ion battery.
Background
The silicon-based material is used as the negative electrode material of the lithium ion battery, has the advantages of rich natural reserve, high safety and lower working platform, and is considered as an ideal choice of the negative electrode material of the lithium ion battery. However, the conductivity is poor, the volume expansion is large in the process of charging and discharging, so that the internal structure of the electrode is collapsed, the electric contact loss and the impedance are increased, and finally, the capacity of the electrode is rapidly attenuated, so that the electrode is used as a negative electrode material of a lithium ion battery. Silicon in its sub-oxidized form, silicon oxide, has been a very promising silicon-based material. Compared with pure silicon, the silicon oxide has higher electrochemical activity in the process of lithium ion intercalation and deintercalation, and the volume expansion effect is much smaller in the charging and discharging processes. The formation of lithium oxide and lithium silicate during the first lithiation helps to buffer the vast volume changes during the subsequent delithiation, thereby extending the cycle life. However, for the micrometer-sized silica particles, there are problems in that a large volume change due to particle pulverization and a decrease in conductivity of lithium ions due to an increase in a transmission distance still occur during the cyclic deintercalation of lithium. Therefore, maintaining the dynamic integrity of the silica microparticles and lithium ion conductivity is critical for their use as silicon-based negative electrode materials.
The silicon oxide-based negative electrode material exhibits poor first-round charge-discharge efficiency due to irreversible reactions occurring during charge-discharge and formation of an SEI film. If the capacity loss associated with the irreversible reaction can be overcome, the silicon oxide based negative electrode material will be an ideal material for high energy density lithium ion negative electrode materials. Many important studies have been made to improve the first round coulombic efficiency (ICE) of the negative electrode materials of the silicon oxide, and the conventional preparation methods of the silicon oxide composite materials mainly obtain silicon oxide/carbon (e.g., silicon oxide/graphite, silicon oxide, carbon nanofibers), silicon oxide/metal (e.g., silicon oxide/lithium, silicon oxide/nickel), silicon oxide/metal oxide (e.g., silicon oxide/ferric oxide, silicon oxide/tin oxide), and porous silicon oxide by solid-phase organic carbon pyrolysis, chemical vapor deposition, magnesia reduction, etc. However, the materials obtained by the methods still have a plurality of problems in practical situations, such as longer lithium ion transmission distance, poor composite effect, more complex production process and the like, and finally the problems of volume expansion and lower initial effect of the silica-based composite material in the circulating process cannot be effectively solved. The material has the problems of short cycle life, poor multiplying power performance, low specific capacity and the like, and severely restricts the wide application of the silicon oxide composite material.
Disclosure of Invention
In order to overcome the problems, the invention adopts micron-sized silicon oxide as a raw material, and the micron-sized silicon oxide and lithium salt are subjected to mechanical ball milling and then are subjected to high-temperature calcination together, and the material is subjected to lithium supplementing through consumption of irreversible components in the calcination process.
In order to achieve the above purpose, the invention adopts the technical scheme that:
a modified preparation method of a lithium ion battery silicon oxide negative electrode material comprises the steps of mixing silicon oxide (SiO) with lithium salt, performing ball milling, and performing high-temperature calcination in an inert atmosphere after ball milling to obtain the modified silicon oxide serving as the lithium ion battery negative electrode material.
Further, grinding micron-sized silicon oxide powder and lithium salt powder in a planetary ball mill for 2-10 hours to obtain solid powder for later use; wherein the mass ratio of the silicon oxide to the lithium salt is 5:1-50:1.
During ball milling, micron-sized silica solid powder, lithium salt solid powder and zirconia balls are added into a ball milling tank, so that the mass ratio of the zirconia balls to the total solid powder (micron-sized silica solid powder and lithium salt solid powder) is 5:1-50:1 in the ball milling process.
The silicon oxide (SiO) is commercially available technical grade silicon oxide (containing a small amount of carbon).
The ball milling direction is alternately forward and reverse once every 30min in the ball milling process, and the intermediate interval time is 10min.
And introducing inert gas into the tubular furnace after ball milling, and calcining at a high temperature of 200-800 ℃ for 1-6h to obtain the modified silicon oxide anode material for the lithium ion battery.
The inert gas can be one of helium, nitrogen and argon.
The lithium salt is fluorine-containing lithium salt.
The lithium salt is lithium difluorooxalate borate (LiDFOB), lithium bistrifluoromethyl sulfonate imide (LiTFSI), lithium bistrifluorosulfonate imide (LiFSI), lithium tetrafluoroborate (LiBF) 4 ) One of them. The invention has the advantages that:
compared with the prior art, the modified lithium ion battery silicon oxide anode material is obtained by using a convenient ball milling method and a high-temperature cracking method. The method can generate lithium-containing interface components by cracking lithium salt, supplements lithium for the material by adjusting the interface composition of the material, and provides additional lithium source for the material in the SEI film forming process, thereby greatly improving the initial coulomb efficiency, the cycling stability and the energy density of the material by supplementing the capacity loss of the material in the initial charge and discharge process. The lithium salt pyrolysis product can be uniformly dispersed in the material by the method, so that the first-round coulomb efficiency and the cycle stability of the material can be effectively improved by the composite material, and the preparation process is high in safety, simple in process, low in cost and easy for industrial production in the synthetic method, and can be widely applied to the fields of electronic products, electric automobiles and the like.
Drawings
FIG. 1 is a scanning electron microscope image of a calcined silica composite material according to an embodiment of the present invention.
FIG. 2 is an X-ray diffraction pattern of a calcined silica composite provided in accordance with an embodiment of the present invention.
Fig. 3 is a charge-discharge graph of the calcined silica composite anode material according to the embodiment of the present invention.
Fig. 4 is a graph showing a comparison of battery performance of the calcined silica composite anode material according to the embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention is further provided in connection with the accompanying examples, and it should be noted that the embodiments described herein are for the purpose of illustration and explanation only, and are not limiting of the invention.
Example 1: mixing 2g of silicon oxide powder with the particle size of about 5 mu m, 0.1g of LiDFOB and 50g of zirconia pellets, placing the mixture in a planetary ball mill for ball milling at 350rpm for 3 hours, taking out the pot, and collecting the powder. The powder was then collected and calcined in a tube furnace at 400 ℃ for 2 hours under argon and the final sample was collected (see fig. 1 and 2). The ball milling adopts a planetary ball mill. Wherein, the ball milling direction is alternately forward and reverse once every 30min in the ball milling process, and the intermediate interval time is 10min.
As can be seen from fig. 1 and 2, the particle size of the calcined silica composite material is about 2 μm, and the surface is uniformly coated with the small-particle lithium salt cleavage product. As shown in fig. 2, the cracking product is LiF, and the interface composition of the material is regulated by using the generation of LiF to supplement lithium to the material, so as to achieve the purpose of modifying the silicon oxide anode material.
Example 2: mixing 2g of silicon oxide powder with the particle size of about 5 mu m, 0.4g of LiDFOB and 50g of zirconia balls, placing the mixture in a ball milling tank for ball milling at 350rpm for 4 hours, taking out the tank, and collecting the powder. Then collecting the powder, introducing argon gas into a tube furnace at 400 ℃ for heat preservation for 3 hours, and collecting a final sample. The ball milling adopts a planetary ball mill. Wherein, the ball milling direction is alternately forward and reverse once every 30min in the ball milling process, and the intermediate interval time is 10min.
Example 3: mixing 2g of silicon oxide powder with the particle size of about 5 mu m, 0.1g of LiDFOB and 50g of zirconia balls, placing the mixture in a ball milling tank for ball milling at 350rpm for 4 hours, taking out the tank, and collecting the powder. Then collecting the powder, introducing argon gas into a tube furnace at 600 ℃ for heat preservation for 6 hours, and collecting a final sample. The ball milling adopts a planetary ball mill. Wherein, the ball milling direction is alternately forward and reverse once every 30min in the ball milling process, and the intermediate interval time is 10min.
Example 4: mixing 2g of silicon oxide powder with the particle size of about 5 mu m, 0.1g of LiDFOB and 50g of zirconia balls, placing the mixture in a ball milling tank for ball milling at 350rpm for 6 hours, taking out the tank, and collecting the powder. Then collecting the powder, introducing argon gas into a tube furnace at 800 ℃ for heat preservation for 4 hours, and collecting a final sample. The ball milling adopts a planetary ball mill. Wherein, the ball milling direction is alternately forward and reverse once every 30min in the ball milling process, and the intermediate interval time is 10min.
Example 5: mixing 2g of silicon oxide powder with the particle size of about 5 mu m, 0.1g of LiTFSI and 50g of zirconia balls, placing the mixture in a ball milling tank for ball milling at 350rpm for 4 hours, taking out the tank, and collecting the powder. Then collecting the powder, introducing argon gas into a tube furnace at 350 ℃ for heat preservation for 3 hours, and collecting a final sample. The ball milling adopts a planetary ball mill. Wherein, the ball milling direction is alternately forward and reverse once every 30min in the ball milling process, and the intermediate interval time is 10min.
Example 6: mixing 2g of silicon oxide powder with the particle size of about 5 mu m, 0.4g of LiTFSI and 50g of zirconia balls, placing the mixture in a ball milling tank for ball milling, taking out the tank after the ball milling is carried out at 350rpm for 8 hours, and collecting the powder. Then collecting the powder, introducing argon gas into a tube furnace at 350 ℃ for heat preservation for 5 hours, and collecting a final sample. The ball milling adopts a planetary ball mill. Wherein, the ball milling direction is alternately forward and reverse once every 30min in the ball milling process, and the intermediate interval time is 10min.
Example 7: mixing 2g of silicon oxide powder with the particle size of about 5 mu m, 0.1g of LiTFSI and 50g of zirconia balls, placing the mixture in a ball milling tank for ball milling at 350rpm for 2 hours, taking out the tank, and collecting the powder. Then collecting the powder, introducing argon gas into a tube furnace at 450 ℃ for heat preservation for 4 hours, and collecting a final sample. The ball milling adopts a planetary ball mill. Wherein, the ball milling direction is alternately forward and reverse once every 30min in the ball milling process, and the intermediate interval time is 10min.
Example 8: mixing 2g of silicon oxide powder with the particle size of about 5 mu m, 0.1g of LiFSI (20:1) and 50g of zirconia balls, placing the mixture into a ball milling tank for ball milling, taking out the tank after 4 hours at the rotating speed of 350rpm, and collecting the powder. Then collecting the powder, introducing argon gas into a tube furnace at 350 ℃ for heat preservation for 1h, and collecting a final sample. The ball milling adopts a planetary ball mill. Wherein, the ball milling direction is alternately forward and reverse once every 30min in the ball milling process, and the intermediate interval time is 10min.
Example 9: mixing 2g of silicon oxide powder with the particle size of about 5 mu m, 0.4g of LiFSI and 50g of zirconia balls, placing the mixture in a ball milling tank for ball milling at 350rpm for 5 hours, taking out the tank, and collecting the powder. Then collecting the powder, introducing argon gas into a tube furnace at 350 ℃ for heat preservation for 3 hours, and collecting a final sample. The ball milling adopts a planetary ball mill. Wherein, the ball milling direction is alternately forward and reverse once every 30min in the ball milling process, and the intermediate interval time is 10min.
Example 10: mixing 2g of silicon oxide powder with the particle size of about 5 mu m, 0.1g of LiFSI and 50g of zirconia balls, placing the mixture in a ball milling tank for ball milling, taking out the tank after 7 hours at 350rpm, and collecting the powder. Then collecting the powder, introducing argon gas into a tube furnace at 450 ℃ for heat preservation for 2 hours, and collecting a final sample. The ball milling adopts a planetary ball mill. Wherein, the ball milling direction is alternately forward and reverse once every 30min in the ball milling process, and the intermediate interval time is 10min.
Example 11: taking 2g of silicon oxide powder with the grain size of about 5 mu m and 0.1g of LiBF 4 And 50g zirconia balls, placing the mixture into a ball milling tank for ball milling at 350rpm for 6 hours, taking out the tank, and collecting powder. Then collecting the powder, introducing argon gas into a tube furnace at 250 ℃ for heat preservation for 4 hours, and collecting a final sample. The ball milling adopts a planetary ball mill. Wherein, the ball milling direction is alternately forward and reverse once every 30min in the ball milling process, and the intermediate interval time is 10min.
Example 12: taking 2g of silicon oxide powder with the grain size of about 5 mu m and 0.1g of LiBF 4 And 50g zirconia balls, placing the mixture into a ball milling tank for ball milling at 350rpm for 8 hours, taking out the tank, and collecting powder. Then collecting the powder, introducing argon gas into a tube furnace at 250 ℃ for heat preservation for 6 hours, and collecting a final sample. The ball milling adopts a planetary ball mill. Wherein, the ball milling direction is alternately forward and reverse once every 30min in the ball milling process, and the intermediate interval time is 10min.
Example 13: taking 2g of silicon oxide powder with the grain size of about 5 mu m and 0.4g of LiBF 4 And 50g of zirconia balls, placing the mixture into a ball milling tank for ball milling at 350rpm for 4 hours, taking out the tank, and collecting powder. Then collecting the powder, introducing argon gas into a tube furnace at 250 ℃ for heat preservation for 4 hours, and collecting a final sample. The ball milling adopts a planetary ball mill. Wherein, the ball milling direction is alternately forward and reverse once every 30min in the ball milling process, and the intermediate interval time is 10min.
Example 14: taking 2g of silicon oxide powder with the grain size of about 5 mu m and 0.1g of LiBF 4 And 50g zirconia balls, placing the mixture into a ball milling tank for ball milling at 350rpm for 2 hours, taking out the tank, and collecting powder. Then collecting the powder, introducing argon gas into a tube furnace at 350 ℃ for heat preservation for 3 hours, and collecting a final sample. The ball milling adopts a planetary ball mill. Wherein, each time in the ball milling processThe ball milling direction is alternated in the forward and reverse directions for 30min, and the intermediate interval time is 10min.
The samples obtained in the above examples 1 to 14 were further scanned by electron microscopy, and all had particle morphology of about 2 μm in size, the surface of which was uniformly coated with SiO by small particles LiF, thereby realizing the regulation and control of the interface components of the material, and effectively supplementing lithium to the material.
Comparative example 1: mixing 2g of silicon oxide powder with the grain size of about 5 mu m and 50g of zirconia balls, placing the mixture into a ball milling tank for ball milling, taking out the tank after the ball milling is carried out at the speed of 350rpm for 2 hours, collecting the powder, grinding the powder, acetylene black and water according to the mass ratio of 8:1:1, taking distilled water as a solvent to prepare suspension, uniformly coating the suspension on a copper foil, transferring the copper foil to an oven for drying at 60 ℃ for 24 hours, cutting the copper foil into pieces with the diameter of 14mm by using a slicer, and transferring the pieces into a glove box for lithium battery assembly. The assembly sequence from bottom to top is CR2032 cathode shell, lithium sheet, diaphragm, lithium battery electrolyte, pole piece, thick steel, shrapnel and CR2032 anode shell. The ball milling adopts a planetary ball mill. Wherein, the ball milling direction is alternately forward and reverse once every 30min in the ball milling process, and the intermediate interval time is 10min.
Comparative example 2: taking 2g of silicon oxide powder with the grain size of about 5 mu m and 0.4g of LiBF 4 (5:1) grinding in a mortar for 1h, and collecting the powder. Then collecting powder, introducing argon gas into a tubular furnace at the temperature of 250 ℃ for heat preservation for 4 hours, collecting a final sample, grinding the final sample, acetylene black and Shuohe according to the mass ratio of 8:1:1, taking distilled water as a solvent to prepare suspension, uniformly coating the suspension on copper foil, transferring the copper foil to an oven at the temperature of 60 ℃ for drying for 24 hours, cutting the copper foil into pieces with the diameter of 14mm by using a slicer, and transferring the pieces to a glove box for lithium battery assembly. The assembly sequence from bottom to top is CR2032 cathode shell, lithium sheet, diaphragm, lithium battery electrolyte, pole piece, thick steel, shrapnel and CR2032 anode shell.
Meanwhile, taking the sample obtained in the example 1 as an example, grinding the obtained sample, acetylene black and Shuohe according to the mass ratio of 8:1:1, taking distilled water as a solvent to prepare suspension, uniformly coating the suspension on copper foil, transferring the copper foil to an oven at 60 ℃ for drying for 24 hours, cutting the copper foil into pieces with the diameter of 14mm by using a slicer, and transferring the pieces to a glove box for assembling a lithium battery. The assembly sequence from bottom to top is CR2032 cathode shell, lithium sheet, diaphragm, lithium battery electrolyte, pole piece, thick steel, shrapnel and CR2032 anode shell.
The batteries assembled using the negative electrode materials obtained in example 1 and comparative examples 1 and 2 were tested, specifically, the blue electric test system for different batteries obtained by assembly was tested at a current density of 0.1C (1c=1200 mA/g) in a voltage range of 0 to 1.5V. The modified silica composite obtained in example 1 had a first round coulombic efficiency of 80%, whereas the unmodified silica had a first round efficiency of only about 70%. After 100 cycles, the modified silica composite had a specific capacity of 730mAh/g, whereas comparative examples 1 and 2 had specific capacities of only 410mAh/g and 300mAh/g, respectively, with a clear difference in performance (see FIGS. 3 and 4). In comparison with example 1, comparative example 1 did not add lithium salt for high temperature calcination cracking and did not generate lithium-containing interfacial components for lithium supplementation of the material, which is why the performance was inferior to example 1. Compared with example 1, the grinding of comparative example 2 only can realize the effect of simply mixing the silicon oxide with the lithium salt, and the cracking product of the lithium salt cannot be uniformly distributed in the silicon oxide, so that lithium cannot be effectively supplemented to the material, which is why the performance of comparative example 2 is poorer than that of example 1.
As can be seen from fig. 3 and 4, the modified preparation of the negative electrode material of silicon oxide according to the present invention greatly improves the initial coulombic efficiency, specific capacity and cycle stability of the negative electrode material of lithium silicon oxide battery as can be seen from performance tests of the batteries respectively assembled in example 1 and comparative example. The obtained modified silicon oxide composite material has micron-sized particle morphology that the surface is uniformly coated with SiO inside by small particles LiF, thereby realizing the regulation and control of material interface components and effectively supplementing lithium to the material.
According to the embodiment of the invention, the lithium salt is cracked after ball milling and high-temperature calcination, the cracked product is uniformly dispersed in the material, a lithium-containing interface component can be generated, the material is supplemented with lithium by adjusting the interface composition of the material, and an additional lithium source is provided for the material in the SEI film forming process, so that the capacity loss of the material in the first-round charge and discharge process is supplemented, and the first-round coulomb efficiency, the cycle stability and the energy density of the material are greatly improved.

Claims (3)

1. A modified preparation method of a lithium ion battery silicon oxide anode material is characterized by comprising the following steps: ball milling micron-sized silicon oxide powder and lithium salt powder in a planetary ball mill for 2-10 hours to obtain solid powder for later use; wherein the mass ratio of the silicon oxide to the lithium salt is 5:1-50:1;
during ball milling, adding micron-sized silica solid powder, lithium salt solid powder and zirconia balls into a ball milling tank, so that the ratio of the zirconia balls to the sum of the mass of the micron-sized silica solid powder and the mass of the lithium salt solid powder is 5:1-50:1 in the ball milling process;
introducing inert gas into the tube furnace after ball milling, and calcining for 1-6 hours at 200-800 ℃ to obtain a modified silicon oxide anode material for a lithium ion battery;
the lithium salt is fluorine-containing lithium salt.
2. The modified preparation method of the lithium ion battery silicon oxide anode material according to claim 1, which is characterized in that: the inert gas is argon.
3. The modified preparation method of the lithium ion battery silicon oxide anode material according to claim 1, which is characterized in that: the lithium salt is lithium difluorooxalate borate (LiDFOB), lithium bistrifluoromethyl sulfonate imide (LiTFSI), lithium bistrifluorosulfonate imide (LiFSI), lithium tetrafluoroborate (LiBF) 4 ) One of them.
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CN109786670A (en) * 2019-01-24 2019-05-21 南开大学 A kind of preparation method of the negative electrode of lithium ionic secondary battery of Gao Shouxiao
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