CN113422020A - Silica material and processing method thereof - Google Patents

Silica material and processing method thereof Download PDF

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Publication number
CN113422020A
CN113422020A CN202110707044.8A CN202110707044A CN113422020A CN 113422020 A CN113422020 A CN 113422020A CN 202110707044 A CN202110707044 A CN 202110707044A CN 113422020 A CN113422020 A CN 113422020A
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beads
grinding
stage
silicon
particle size
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Inventor
刘东海
王志勇
陈红
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Hunan Shinzoom Technology Co ltd
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Hunan Shinzoom Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—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
    • 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 application relates to the field of silica materials, in particular to a silica material and a processing method thereof. Carrying out first-stage grinding on the silicon oxide particles at the temperature of 400-600 ℃ in an inert atmosphere; then cracking the reducing gas containing the carbon element in the mixed atmosphere of inert gas and the reducing gas containing the carbon element at the temperature of 700-1000 ℃, and carrying out second-stage grinding until the grain diameter of the silicon-oxygen grains D50 is 500nm-2 μm. The grinding conditions of different grinding stages are controlled, so that the silica particles can be crushed, the silica particles can be coated, and the air stability and the electrochemical performance of the crushed silica particles are improved. The treatment process is simple in flow, simple and easy to operate and easy for batch production.

Description

Silica material and processing method thereof
Technical Field
The application relates to the field of silica materials, in particular to a silica material and a processing method thereof.
Background
Silicon-based negative electrode materials have an ultrahigh specific capacity and become an ideal choice for lithium ion battery negative electrode materials, but how to reduce the volume expansion of silicon-oxygen materials and how to improve the electrochemical performance of silicon-oxygen materials are always problems to be overcome.
The application aims to provide a treatment method of a silica material, and aims to improve the first effect of a lithium battery after the silica material is used for the lithium battery.
Disclosure of Invention
The embodiment of the application aims to provide a silicon-oxygen material and a processing method thereof, and aims to improve the first efficiency of a lithium battery prepared from the silicon-oxygen material.
In a first aspect, the present application provides a method for treating a silicon oxygen material, comprising:
carrying out first-stage grinding on the silicon oxide particles at the temperature of 400-600 ℃ in an inert atmosphere; then, the second stage grinding is carried out in the mixed atmosphere of inert gas and reducing gas containing carbon element at the temperature of 700-1000 ℃ to crack the reducing gas containing carbon element, and the silicon oxide particles D50 are ground until the particle size is 500nm-2 μm.
Grinding the silica particles at 400-600 ℃, and then grinding again in the mixed atmosphere of reducing gas containing carbon element and inert gas; the grinding conditions of different grinding stages are controlled, so that the silica particles can be crushed, the particles can be coated, and the air stability and the electrochemical performance of the crushed silica particles are improved. The two-stage grinding process is controlled to make the particle diameter of the final silicon oxide particle D50 be 500nm-2 μm, so that the length of an electron transmission path can be shortened. The method has the advantages of simple preparation process flow, simple and easy operation and easy batch production.
In some embodiments of the first aspect of the present application, the step of performing the first-stage grinding of the silicon oxide particles at 400-600 ℃ in an inert atmosphere comprises: the silicon oxide particles are placed in a grinding cavity, and the temperature is raised to 400-600 ℃ at the speed of 1-10 ℃/min.
In some embodiments of the first aspect of the present application, after the step of first-stage polishing of the silicon oxide particles at 400-600 ℃ in an inert atmosphere, the temperature is raised to 700-1000 ℃ at a rate of 1-10 ℃/min.
In some embodiments of the first aspect of the present disclosure, the elemental carbon-containing reducing gas is selected from at least one of methane, ethane, propane, ethylene, and acetylene.
In some embodiments of the first aspect of the present application, the silica particles have a D50 particle size of 2 to 5 μm prior to the first stage grinding.
In some embodiments of the first aspect of the present application, the first stage and second stage milling is performed with the silica particles using ball milling beads in the following size ratios;
big beads with the particle size of 8-14 mm;
medium beads with the particle size of 2-8 mm; and
beads with a particle size of 0.2-2 mm;
the mass ratio of the big beads to the medium beads to the small beads is (0-2): (2-5): (3-8).
In some embodiments of the first aspect of the present application, the first stage milling has a milling speed of 10 to 80 rpm and a milling time of 5 to 30 hours;
the grinding speed of the second stage grinding is 5-30 r/min, the main purpose is to control the crushing degree of the material and prevent the material from accumulating, and the grinding time is 2-20 h.
In some embodiments of the first aspect of the present application, the first stage milling further comprises a coarse milling stage of silica particles having a D50 of 5 to 15 μm using the following size ratios of ball milling beads:
big beads with the particle size of 8-14 mm;
medium beads with the particle size of 2-8 mm; and
beads with a particle size of 0.2-2 mm;
the mass ratio of the big beads to the medium beads to the small beads is (0-2): (2-5): (3-8).
In some embodiments of the first aspect of the present application, the rotation speed in the rough grinding stage is 20-100 rpm and the grinding time is 0.2-4 h.
In a second aspect, the present application provides a silicon oxygen material, which is prepared by the above-mentioned processing method of silicon oxygen material.
The silica material electron transmission path that this application improved is shorter, and can avoid the irreversible reaction of silica material and oxygen under the carbon cladding, can effectively improve first effect.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The silicon oxide material and the processing method thereof according to the embodiments of the present application will be specifically described below.
A method of treating a silicon oxygen material comprising: carrying out first-stage grinding on the silicon oxide particles at the temperature of 400-600 ℃ in an inert atmosphere; then, the second stage grinding is carried out in the mixed atmosphere of inert gas and reducing gas containing carbon element at the temperature of 700-1000 ℃ to crack the reducing gas containing carbon element, and the silicon oxide particles D50 are ground until the particle size is 500nm-2 μm.
Grinding the silicon oxide particles in two stages, wherein the first stage is grinding in an inert atmosphere at the temperature of 400-600 ℃; the second stage is grinding in the mixed atmosphere of reducing gas containing carbon element and inert gas at the temperature of 700-1000 ℃.
After the two-stage grinding, the grain diameter of the silicon oxide grain D50 is 500nm-2 μm.
In the present application, the molecular formula of the silicon oxygen material is SiOx(x is more than 0 and less than 2), and the main structure of the silicon-oxygen material is that silicon nano-crystalline particles are dispersed in silicon dioxide.
The grinding process of the two stages is controlled, the particle size of the final silica particles D50 is 500nm-2 μm, the conductivity of the silica material is poor, when the silica material is used as a negative electrode material, the polarization of the battery is aggravated due to the overlarge particle size, the dynamic performance of the battery is poor, the particle size is reduced, the transmission path of ions can be effectively shortened, the polarization of the material is reduced, and the electrochemical performance of the material is improved.
In some embodiments of the present application, the two-stage milling is performed with a material having a particle size of 2-5 μm selected from the silicon oxide particles D50, for example, the particle size of D50 may be 2 μm, 3 μm, 3.2 μm, 4 μm, 5 μm, and so on. In other words, the silica particles D50 had a particle size of 2 to 5 μm before the first stage grinding.
In some embodiments of the present application, the first and second stages of milling are performed using macrobeads, mesobeads, and beads with silica particles.
The beads have a particle size of 8 to 14mm, and may be, for example, 8mm, 9mm, 10mm, 11mm, 13mm or 14mm, and the like.
The particle size of the medium beads is 2 to 8mm, and may be, for example, 2mm, 3mm, 5mm, 6mm, 8mm, or the like.
The beads have a particle size of 0.2 to 2mm, and may be, for example, 0.2mm, 0.6mm, 0.8mm, 1.3mm, 1.7mm, 2mm, or the like.
The mass ratio of the big beads to the medium beads to the small beads is (0-2): (2-5): (3-8), for example, the ratio of 0.1:2:3, 1:2:3, 1.4:3.1:5.5, 2:5:8, 1.5:4:7, etc.
The grinding beads with the size ratio can further crush silica particles, and meanwhile, the situation that the particle size of the crushed silica particles is too small or too large is avoided.
The first stage of grinding is carried out at the temperature of 400-600 ℃ in an inert atmosphere; for example, the inert gas atmosphere may be nitrogen, helium, etc., and the temperature may be 400 ℃, 420 ℃, 460 ℃, 500 ℃, 510 ℃, 530 ℃, 580 ℃, 590 ℃, 600 ℃, etc.
In some embodiments of the present application, the silica particles are placed in a milling chamber, such as a ball mill, and heated to 400 ℃ at a rate of 1-10 ℃/min to 600 ℃, for example, the heating rate can be 1 ℃/min, 2 ℃/min, 5 ℃/min, 7 ℃/min, 9 ℃/min, 10 ℃/min.
Illustratively, the rotation speed during the grinding process is 10-80 rpm, for example, 10 rpm, 15 rpm, 18 rpm, 23 rpm, 36 rpm, 42 rpm, 53 rpm, 68 rpm, 80 rpm.
Illustratively, the time for the first stage milling may be 5-30h, e.g., 5h, 8h, 11h, 16h, 21h, 23h, 26h, 27h, 30 h.
The silicon crystal grains dispersed in the silicon dioxide material can be prevented from being oxidized to form silicon dioxide by grinding at 400-600 ℃ in an inert atmosphere, so that the first effect and the capacity are prevented from being reduced.
The examples of the present application show a process for preparing silicone particles of D50 having a particle size of 2 to 5 μm: grinding silica raw material with D50 of 5-15 μm by ball milling to obtain silica particles.
In the present embodiment, the ball-milled beads include large beads, medium beads and small beads, wherein the sizes and proportions of the large beads, the medium beads and the small beads are referred to above and will not be described herein again.
For example, in the process of grinding the silicon oxygen raw material, the rotation speed is 20 to 100 revolutions/min, for example, 20 revolutions/min, 25 revolutions/min, 37 revolutions/min, 47 revolutions/min, 54 revolutions/min, 63 revolutions/min, 73 revolutions/min, 85 revolutions/min, 94 revolutions/min, and 100 revolutions/min.
The method for preparing the silica particles with the particle size of 2-5 mu m of D50 is simple in treatment method, and can greatly save the cost when being used in industry.
In other embodiments of the present application, the silica particles with a particle size of D50 of 2-5 μm may be obtained by other methods, such as sieving or purchasing.
And after the first-stage grinding is finished, performing second-stage grinding, wherein the second-stage grinding is performed in a mixed atmosphere of reducing gas containing carbon elements and inert gas at the temperature of 700-1000 ℃.
Illustratively, the reducing gas containing carbon elements is selected from at least one of methane, ethane, propane, ethylene, and acetylene.
For example, the volume ratio of the reducing gas containing carbon element and the inert gas in the mixed atmosphere may be 1:5.
Illustratively, the temperature during the second stage grinding process may be 700 ℃, 720 ℃, 790 ℃, 800 ℃, 830 ℃, 850 ℃, 900 ℃, 960 ℃, 990 ℃, 1000 ℃, and so on.
Illustratively, the second stage grinding time may be 2-20h, such as 2h, 3h, 5h, 9h, 12h, 16h, 18h, 20h, and the like.
In the embodiment of the present application, after the first stage polishing is completed, the temperature is raised to 700-. For example, the temperature ramp rate can be 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 5 deg.C/min, 7 deg.C/min, 10 deg.C/min, and the like.
Illustratively, in some embodiments of the present application, the second stage grinding is performed at a speed of 5-30 rpm, such as 5 rpm, 7 rpm, 9 rpm, 12 rpm, 17 rpm, 21 rpm, 23 rpm, 26 rpm, 29 rpm, 30 rpm, or the like.
In the second grinding stage, carbon generated after the reducing gas containing the carbon element is cracked at high temperature is deposited on the surface of the silica particles; a carbon protective layer is formed on the surface of the silica particles in the crushing process, so that the first effect and the capacity reduction caused by the oxidation of crystal grains are avoided.
The silica material is easy to react with oxygen in the air to cause loss, so that common silica single particles can be only crushed to about 5 mu m, the silica material with smaller particle size is obtained by grinding in two stages, and the oxidation is avoided in the whole process, thereby being beneficial to improving the electrochemical performance of the silica material. The processing method of the silicon oxygen material provided by the embodiment of the application has at least the following advantages:
carrying out first-stage grinding at 400-600 ℃, and then carrying out second-stage grinding in a mixed atmosphere of reducing gas containing carbon element and inert gas; the grinding conditions of different grinding stages are controlled, so that the silica particles can be crushed, the particles can be coated at the same time, the air stability and the electrochemical performance of the crushed silica particles are improved, the particle size of the final silica particles D50 is 500nm-2 mu m through two-stage grinding, the length of an electronic transmission path can be effectively shortened, and the electrical performance is improved. The method has the advantages of simple preparation process flow, simple and easy operation and easy batch production.
The application also provides a silicon-oxygen material prepared by the processing method of the silicon-oxygen material.
The silica material electron transmission path that this application improved is shorter, and can avoid the irreversible reaction of silica material and oxygen under the carbon cladding, can effectively improve first effect.
The silica material provided by the application is relatively stable, and has relatively high first effect and relatively large capacity.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
This example provides a silicon oxygen material, which is prepared by the following steps:
1) taking 500g D50 silica particles with the diameter of 45 mu m; taking zirconia ball grinding beads with the diameter of 12mm, zirconia ball grinding beads with the diameter of 8mm and zirconia ball grinding beads with the diameter of 3mm, wherein the mass ratio of the zirconia ball grinding beads to the zirconia ball grinding beads with the diameter of 3mm is 2:2: 3; the total mass of the ball milling beads is 1kg, silica particles and the ball milling beads are mixed, the rotating speed of the ball mill is 20 r/min, and the ball milling time is 4 h.
2) Putting the silica and the ball-milling beads in the step 1) into a rotary furnace, heating to 400 ℃ at a heating rate of 10 ℃/min, and grinding for 30 hours at a rotating speed of 80 r/min of the rotary furnace.
3) The temperature is raised to 900 ℃ at the temperature raising rate of 9 ℃/min, and the rotating speed of the rotary furnace is 30 revolutions per minute for grinding for 2 hours.
Wherein, methane and nitrogen with the volume ratio of 5:1 are introduced into the rotary furnace in the step 2) and the step 3).
Example 2
This example provides a silicon oxygen material, which is prepared by the following steps:
1) taking silica particles with 600g D50 being 45 mu m; taking zirconia ball grinding beads with the diameter of 12mm, zirconia ball grinding beads with the diameter of 8mm and zirconia ball grinding beads with the diameter of 3mm, wherein the mass ratio of the zirconia ball grinding beads to the zirconia ball grinding beads with the diameter of 3mm is 2:2: 3; the total mass of the ball milling beads is 1.3kg, silica particles and the ball milling beads are mixed, the rotating speed of the ball mill is 100 r/min, and the ball milling time is 0.2 h.
2) Putting the silica and the ball-milling beads in the step 1) into a rotary furnace, heating to 400 ℃ at a heating rate of 5 ℃/min, and grinding for 30 hours at a rotating speed of 105 r/min of the rotary furnace.
3) The temperature is raised to 700 ℃ at the heating rate of 10 ℃/min, and the rotating speed of the rotary furnace is 30 revolutions per minute for grinding for 10 hours.
Wherein, acetylene and nitrogen with the volume ratio of 1:5 are introduced into the rotary furnace in the steps 2) and 3).
Example 3
This example provides a silicon oxygen material, which is prepared by the following steps:
1) taking 500g D50 silica particles with the diameter of 45 mu m; taking 14mm zirconia ball grinding beads, 2mm zirconia ball grinding beads and 2mm zirconia ball grinding beads, wherein the mass ratio of the zirconia ball grinding beads to the 2mm zirconia ball grinding beads is 1: 3: 6; the total mass of the ball milling beads is 1kg, silica particles and the ball milling beads are mixed, the rotating speed of the ball mill is 100 r/min, and the ball milling time is 4 h.
2) Putting the silica and the ball-milling beads in the step 1) into a rotary furnace, heating to 600 ℃ at a heating rate of 10 ℃/min, and grinding for 30 hours at a rotation speed of 10 r/min.
3) The temperature is raised to 850 ℃ at the heating rate of 10 ℃/min, and the rotating speed of the rotary furnace is 5 revolutions per minute for grinding for 10 hours.
Wherein, the propylene and the nitrogen with the volume ratio of 1:5 are introduced into the rotary furnace in the step 2) and the step 3).
Example 4
This example provides a silicon oxygen material, which is prepared by the following steps:
1) taking 500g D50 silica particles with the diameter of 45 mu m; taking 11mm zirconia ball grinding beads, 2mm zirconia ball grinding beads and 0.2mm zirconia ball grinding beads, wherein the mass ratio of the 11mm zirconia ball grinding beads to the 2mm zirconia ball grinding beads to the 0.2mm zirconia ball grinding beads is as follows: 5: 3; the total mass of the ball milling beads is 1kg, silica particles and the ball milling beads are mixed, the rotating speed of the ball mill is 60 r/min, and the ball milling time is 1.2 h.
2) Putting the silica and the ball-milling beads in the step 1) into a rotary furnace, heating to 500 ℃ at a heating rate of 7 ℃/min, and grinding for 20 hours at a rotating speed of 60 revolutions per minute of the rotary furnace.
3) The temperature is raised to 900 ℃ at the temperature raising rate of 8 ℃/min, and the rotating speed of the rotary furnace is 25 revolutions per minute for grinding for 8 hours.
Wherein, methane and nitrogen with the volume ratio of 1:5 are introduced into the rotary furnace in the step 2) and the step 3).
Example 5
This example provides a silicon oxygen material, which is prepared by the following steps:
1) taking 500g D50 silica particles with the diameter of 45 mu m; taking 13mm zirconia ball grinding beads, 8mm zirconia ball grinding beads and 2mm zirconia ball grinding beads, wherein the mass ratio of the zirconia ball grinding beads to the 8mm zirconia ball grinding beads to the 2mm zirconia ball grinding beads is 0.7: 2: 4; the total mass of the ball milling beads is 1kg, silica particles and the ball milling beads are mixed, the rotating speed of the ball mill is 54 r/min, and the ball milling time is 3 h.
2) Putting the silica and the ball-milling beads in the step 1) into a rotary furnace, wherein in the first stage, the temperature is increased to 500 ℃ at the temperature increase rate of 8 ℃/min, and the rotary furnace is rotated at the speed of 70 r/min for grinding for 10 h.
3) The temperature is raised to 800 ℃ at the heating rate of 7 ℃/min, and the rotating speed of the rotary furnace is 24 r/min for grinding for 4 h.
Wherein, methane and nitrogen with the volume ratio of 1:5 are introduced into the rotary furnace in the step 2) and the step 3).
Comparative example 1
The present comparative example provides a silicone material, see example 1, with comparative example 1 differing from example 1 in that:
taking out grinding beads in the step 2), and carrying out the step 2) and the step 3) under a non-grinding state; the process parameters of step 2) and step 3) are the same as in example 1.
Comparative example 2
The present comparative example provides a silicone material, see example 1, and comparative example 2 differs from example 1 in that:
step 1), step 2) and step 3) are all carried out under a nitrogen atmosphere.
Comparative example 3
The present comparative example provides a silicone material, see example 1, and comparative example 3 differs from example 1 in that the steps after step 1) are completed are as follows:
2) putting the silica and the ball-milling beads in the step 1) into a rotary furnace, introducing methane and nitrogen in a volume ratio of 1:5 into the rotary furnace, and grinding for 2 hours at the rotating speed of the rotary furnace of 30 revolutions per minute.
Comparative example 4
The comparative example provides a silicone material made essentially by the steps of:
taking 500g D50 silica particles with the diameter of 45 mu m; taking zirconia ball grinding beads with the diameter of 12mm, zirconia ball grinding beads with the diameter of 8mm and zirconia ball grinding beads with the diameter of 3mm, wherein the mass ratio of the zirconia ball grinding beads to the zirconia ball grinding beads with the diameter of 3mm is 2:2: 3; the total mass of the ball milling beads is 1kg, silica particles and the ball milling beads are mixed, and three-stage ball milling is carried out: a first stage: the rotating speed of the ball mill is 20 r/min, the ball milling time is 4h, and the second stage: grinding for 30h at the rotating speed of 80 revolutions per minute, and carrying out a third stage: grinding for 2h at the rotating speed of 30 r/min, wherein the ball milling atmosphere is air atmosphere, and obtaining the final ball milling material.
Examples of the experiments
Examples 1 to 5 and comparative examples 1 to 4 were examined.
(1) And (3) morphology testing: carrying out morphology detection on the graphite composite material prepared in the example 1 by adopting a scanning electron microscope (SEM, SU81510 type);
(2) testing the particle size distribution of the material: d50 test of the resulting material the material was obtained from the malvern 3000 instrument test.
(3) Testing material capacity and first effect: uniformly mixing the obtained negative electrode material with SBR, CMC and SP in a ratio of 85:3.2:1.8:10, coating the mixture on a copper foil, preparing a pole piece with the diameter of 12mm by drying, rolling and cutting, and assembling the pole piece and a metal lithium piece into a button cell, wherein the electrolyte is the electrolyte of a conventional lithium ion battery, and the diaphragm is a PP diaphragm. Electrochemical performance testing conventional battery charging and discharging was performed on a blue tester. The capacity of the negative electrode material is the half-cell delithiation capacity to capacity ratio measured at a rate of 0.1C.
(4) The test protocol for the cycling performance of the material is as follows: firstly, mixing the obtained negative electrode material with a commercial graphite negative electrode material with the capacity of 350mAh/g to prepare a silica/graphite composite negative electrode material with the capacity of 500mAh/g, then uniformly mixing the composite material with SBR, CMC and SP in a ratio of 94.5:2.5:1.5:1.5, coating the mixture on a copper foil, preparing a pole piece with the diameter of 12mm through drying, rolling and cutting, and assembling the pole piece and a metal lithium piece into a button cell, wherein the electrolyte is the electrolyte of a conventional lithium ion battery, and the diaphragm is a PP diaphragm. Electrochemical performance testing conventional battery charging and discharging was performed on a blue tester.
The test results are shown in table 1.
TABLE 1
Figure BDA0003132067640000111
As can be seen from table 1:
(1) the method provided by the embodiment of the application can effectively reduce the particle size of the silica material, prepare the silica material with submicron size, and compared with the silica material with large particle size, the silica material can be mixed with graphite to be used as the negative electrode material of the lithium ion battery, so that the cycle stability and the quick charging performance of the material can be effectively improved.
(2) The method provided by the application reduces the particle size of the particles in an inert atmosphere, and introduces the carbon protection layer structure in the preparation process, so that the damage of oxygen to the material structure can be effectively avoided, and the material capacity and the first effect are ensured. The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. A method for treating a silicon-oxygen material, comprising:
carrying out first-stage grinding on the silicon oxide particles at the temperature of 400-600 ℃ in an inert atmosphere; then the
Cracking the reducing gas containing the carbon element in the mixed atmosphere of inert gas and the reducing gas containing the carbon element at the temperature of 700-1000 ℃, and carrying out second-stage grinding until the grain diameter of the silicon oxide grains D50 is 500nm-2 μm.
2. The method for processing a silicon/oxygen material as claimed in claim 1, wherein the step of performing the first-stage polishing on the silicon/oxygen particles at 400-600 ℃ in an inert atmosphere comprises: the silicon oxide particles are placed in a grinding cavity, and the temperature is raised to 400-600 ℃ at the speed of 1-10 ℃/min.
3. The method for processing a silicon oxide material as claimed in claim 1, wherein the temperature rise rate is 1-10 ℃/min and the temperature rises to 700-1000 ℃ after the step of first-stage polishing the silicon oxide particles at 400-600 ℃ in an inert atmosphere.
4. The method for treating a silicon oxygen material according to claim 1, wherein the reducing gas containing a carbon element is at least one selected from methane, ethane, propane, ethylene, and acetylene.
5. The method of processing a silicone material according to claim 1, wherein the particle size of D50 of the silicone particles before the first stage grinding is 2 to 5 μm.
6. The method of processing a silica material according to any one of claims 1 to 5, wherein the first and second stage milling is carried out with the silica particles using ball milling beads in the following size ratios;
big beads with the particle size of 8-14 mm;
medium beads with the particle size of 2-8 mm; and
beads with a particle size of 0.2-2 mm;
the mass ratio of the big beads to the medium beads to the small beads is (0-2): (2-5): (3-8).
7. The method for treating a silicon/oxygen material according to claim 6, wherein the first-stage polishing is performed at a polishing rate of 10 to 80 rpm for 5 to 30 hours;
the grinding speed of the second stage of grinding is 5-30 r/min, and the grinding time is 2-20 h.
8. The method for treating a silicon oxygen material according to any one of claims 1 to 5, wherein the first stage grinding is preceded by a coarse grinding stage of silicon oxygen particles with D50 of 5 to 15 μm using ball milling beads of the following size ratios:
big beads with the particle size of 8-14 mm;
medium beads with the particle size of 2-8 mm; and
beads with a particle size of 0.2-2 mm;
the mass ratio of the big beads to the medium beads to the small beads is (0-2): (2-5): (3-8).
9. The method for treating a silicon/oxygen material according to claim 8, wherein the rotation speed in the rough grinding stage is 20 to 100 rpm, and the grinding time is 0.2 to 4 hours.
10. A silicone material, characterized in that it is obtained by a process for the treatment of a silicone material according to any one of claims 1 to 9.
CN202110707044.8A 2021-06-24 2021-06-24 Silica material and processing method thereof Pending CN113422020A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111029534A (en) * 2019-12-06 2020-04-17 浙江埃登达新能源材料有限公司 Production device for ball mill negative electrode bag
CN111180719A (en) * 2020-01-07 2020-05-19 马鞍山科达普锐能源科技有限公司 Method for preparing nano silicon by three-stage grinding
CN111384380A (en) * 2018-12-29 2020-07-07 上海杉杉科技有限公司 Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery prepared from silicon-carbon negative electrode material
CN111755684A (en) * 2020-07-06 2020-10-09 马鞍山科达普锐能源科技有限公司 Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof
CN112510180A (en) * 2020-12-02 2021-03-16 江苏科技大学 Silicon oxide-carbon filament active material and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111384380A (en) * 2018-12-29 2020-07-07 上海杉杉科技有限公司 Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery prepared from silicon-carbon negative electrode material
CN111029534A (en) * 2019-12-06 2020-04-17 浙江埃登达新能源材料有限公司 Production device for ball mill negative electrode bag
CN111180719A (en) * 2020-01-07 2020-05-19 马鞍山科达普锐能源科技有限公司 Method for preparing nano silicon by three-stage grinding
CN111755684A (en) * 2020-07-06 2020-10-09 马鞍山科达普锐能源科技有限公司 Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof
CN112510180A (en) * 2020-12-02 2021-03-16 江苏科技大学 Silicon oxide-carbon filament active material and preparation method and application thereof

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Application publication date: 20210921