CN114744166A - Preparation method of pre-lithiated silica composite material - Google Patents
Preparation method of pre-lithiated silica composite material Download PDFInfo
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- CN114744166A CN114744166A CN202210177732.2A CN202210177732A CN114744166A CN 114744166 A CN114744166 A CN 114744166A CN 202210177732 A CN202210177732 A CN 202210177732A CN 114744166 A CN114744166 A CN 114744166A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 79
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007773 negative electrode material Substances 0.000 claims abstract description 53
- 238000003763 carbonization Methods 0.000 claims abstract description 43
- 239000010426 asphalt Substances 0.000 claims abstract description 22
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- 229910052744 lithium Inorganic materials 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- 238000000462 isostatic pressing Methods 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 230000004927 fusion Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 9
- -1 alkyl lithium Chemical compound 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 3
- 102220043159 rs587780996 Human genes 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 13
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000010410 layer Substances 0.000 abstract description 10
- 239000011247 coating layer Substances 0.000 abstract description 9
- 238000006138 lithiation reaction Methods 0.000 abstract description 5
- 230000002829 reductive effect Effects 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 abstract description 2
- 239000011258 core-shell material Substances 0.000 abstract description 2
- 150000002642 lithium compounds Chemical class 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 239000010405 anode material Substances 0.000 description 7
- 230000005389 magnetism Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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 discloses a preparation method of a pre-lithiated silica composite material, which comprises the following steps: mixing materials, making blocks, primary carbonization and secondary carbonization. The pre-lithiation silica-oxygen composite negative electrode material prepared by the method has a multi-layer core-shell structure, asphalt, a lithium compound and silicon oxide are tightly attached together in a briquetting mode, so that the pre-lithiation reaction is accelerated, meanwhile, the asphalt forms a first compact coating layer on the surface of the pre-lithiation silicon oxide, and then a layer of uniform amorphous carbon is coated on the surface of the existing compact coating layer through gas phase coating, and the possibility of the pre-lithiation silica-oxygen composite material contacting with a binder is effectively reduced through double-layer compact uniform coating layers; the lithium ion battery assembled by the pre-lithiated silica-oxygen composite material with the specific structure has excellent first coulombic efficiency, first reversible capacity and high cycle stability; and the preparation process is simple, the operation is convenient, and the production equipment is few, so that the cost is reduced, the popularization and the application are convenient, and the method is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of silica composite materials, in particular to a preparation method of a pre-lithiated silica composite material.
Background
In order to meet the large-scale energy storage requirement in the new energy field, the new-generation lithium ion battery requires that an electrode active material has higher volume and weight specific capacity to further realize high volume energy density and high quality energy density. New high capacity silicon oxygen negative electrode materials have been produced since commercialization of graphite negative electrodes, however, they lose a large amount of active lithium due to SEI film formation at the time of first charge and discharge, and are first inefficient, which limits their widespread use.
Currently, an effective approach to solving such problems is the prelithiation technique, which increases the initial coulombic efficiency, cycle capacity, cycle life, and actual energy density of the battery by compensating for the loss of first irreversible lithium in the electrode material. However, the existing pre-lithiated silica materials have poor processability mainly because the materials are alkaline and react with a binder during slurry preparation, so that the coated particles are large in quantity and the binding is not firm, and finally, the comprehensive performance of the battery is poor.
CN113948688A discloses a modified pre-lithiated silica composite material, a preparation method and an application thereof, and the method comprises the following steps: s1, uniformly mixing the disproportionated SiO x and the lithium-containing compound in a protective atmosphere, and roasting in a protective gas atmosphere or under a vacuum condition to obtain a pre-lithiated silica composite material; s2, placing the pre-lithiated silica-oxygen composite material prepared in the step S1 in a mixed atmosphere containing a silicon source, and roasting at high temperature to obtain a pre-lithiated silica-oxygen composite material with a surface coated with a silicon layer; and S3, blending the pre-lithiated silica-oxygen composite material with the surface coated with the silicon layer and prepared in the step S2 with an organic carbon source, and calcining at high temperature to perform carbon coating treatment to obtain the modified pre-lithiated silica-oxygen composite material. The method has complex steps, multi-step heat treatment, high energy consumption and difficult industrial application due to the use of dangerous silicon source gas.
CN109888266A discloses a silicon-based negative plate, a preparation method thereof and a lithium ion battery. The negative electrode coating of the silicon-based negative electrode plate comprises a first coating positioned on a current collector and a second coating positioned on the first coating, wherein an active substance in the first coating comprises a silicon-based negative electrode material, an active substance in the second coating does not comprise the silicon-based negative electrode material, and the surface of the second coating contains lithium. The preparation method comprises the steps of 1) coating a first slurry containing a silicon-based negative electrode material on a current collector to form a first coating; 2) forming a second coating layer on the first coating layer with a second slurry not containing a silicon-based anode material; 3) and pre-doping lithium to the pole piece containing the second coating to obtain the silicon-based negative pole piece. Compared with powder treatment, the method is complex in process, difficult to control and not beneficial to industrialization.
Therefore, there is a need for a new method to improve the existing methods for preparing pre-lithiated silica composites for lithium batteries.
Disclosure of Invention
In view of the above, the present invention is directed to the defects existing in the prior art, and the main object of the present invention is to provide a method for preparing a pre-lithiated silica composite material, which has the advantages of simple process, convenient operation, less production equipment, capability of further reducing the cost, convenience for popularization and application, and suitability for large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a pre-lithiated silica composite material comprises the following steps:
(1) mixing materials:
adding silicon oxide, a reducing lithium-containing compound and a binder into a mechanical fusion machine according to a certain proportion, and treating for 5-20min to obtain a precursor of the silica composite negative electrode material;
(2) block making:
putting the precursor of the silicon-oxygen composite negative electrode material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 100-300MPa, so as to obtain an isostatic block;
(3) primary carbonization:
putting the isostatic block obtained in the step (2) into a nitrogen atmosphere protective furnace for primary carbonization, raising the temperature to 400-1000 ℃ at the heating rate of 2-25 ℃/min, preserving the heat for 4-10 hours, and mechanically crushing until D50 is 3-8 mu m to obtain a silicon-oxygen composite negative electrode material after primary carbonization;
(4) secondary carbonization:
and (4) placing the silicon-oxygen composite negative electrode material subjected to the primary carbonization in the step (3) in an atmosphere furnace filled with an organic carbon source for secondary carbonization, raising the temperature to 600-900 ℃ at the heating rate of 10-30 ℃/min, preserving the temperature for 1-5 hours, and removing magnetism and screening to obtain the pre-lithiated silicon-oxygen composite negative electrode material.
Preferably, the silicon oxide in step (1) is SiOxWherein x is more than 0 and less than 2, and D50 is 2-5 mu m.
As a preferable scheme, the reducing lithium-containing compound in step (1) is one or a mixture of lithium hydride, alkyl lithium, metallic lithium, lithium aluminum hydride and lithium amide.
Preferably, the binder in step (1) is one or a mixture of two of coal-series asphalt and oil-series asphalt, and the softening point of the binder is 50-200 ℃.
As a preferable scheme, the mass ratio of the silicon oxide, the reduced lithium-containing compound and the binder in the step (1) is 100 (0.5-10) to (0.5-5).
As a preferable scheme, the organic carbon source in the step (4) is one or a mixture of several of methane, ethylene, acetylene and benzene.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and specifically, the technical scheme includes that:
the pre-lithiated silica composite negative electrode material prepared by the preparation method has a multi-layer core-shell structure, firstly, asphalt, a lithium compound and silicon oxide are tightly attached together in a briquetting mode, so that the pre-lithiation reaction is accelerated, meanwhile, the asphalt forms a first layer of compact coating layer on the surface of the pre-lithiated silicon oxide, secondly, a layer of uniform amorphous carbon is coated on the surface of the existing compact coating layer through gas phase coating, and the possibility of the pre-lithiated silica composite material contacting with a binder is effectively reduced through double layers of compact and uniform coating layers; the lithium ion battery assembled by the pre-lithiated silica-oxygen composite material with the specific structure has excellent first coulombic efficiency, first reversible capacity and high cycle stability; moreover, the preparation method has the advantages of simple process, convenient operation and less production equipment, thereby further reducing the cost, being convenient for popularization and application and being suitable for large-scale production.
The present invention will be described in detail with reference to specific embodiments in order to more clearly illustrate the structural features and effects of the present invention.
Detailed Description
The invention discloses a preparation method of a pre-lithiated silica composite material, which comprises the following steps:
(1) mixing materials:
adding silicon oxide, a reducing lithium-containing compound and a binder into a mechanical fusion machine according to a certain proportion, and treating for 5-20min to obtain a silica composite anode material precursor; the mass ratio of the silicon oxide, the reducing lithium-containing compound and the binding agent is 100 (0.5-10) to (0.5-5); the silicon oxide is SiOxWherein x is more than 0 and less than 2, and D50 is 2-5 mu m; the reducing lithium-containing compound is one or a mixture of lithium hydride, alkyl lithium, metallic lithium, lithium aluminum hydride and lithium amide; the binder is one or a mixture of two of coal-series asphalt and oil-series asphalt, and the softening point of the binder is 50-200 ℃.
(2) And (3) blocking:
and (2) putting the precursor of the silicon-oxygen composite negative electrode material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 100-300MPa, so as to obtain an isostatic pressed block.
(3) Primary carbonization:
and (3) putting the isostatic block obtained in the step (2) into a nitrogen atmosphere protective furnace for primary carbonization, raising the temperature to 400-1000 ℃ at the heating rate of 2-25 ℃/min, preserving the heat for 4-10 hours, and mechanically crushing until D50 is 3-8 mu m to obtain the primary carbonized silicon-oxygen composite negative electrode material.
(4) Secondary carbonization:
placing the silicon-oxygen composite negative electrode material subjected to the primary carbonization obtained in the step (3) in an atmosphere furnace filled with an organic carbon source for secondary carbonization, raising the temperature to 600-900 ℃ at the heating rate of 10-30 ℃/min, preserving the heat for 1-5 hours, and carrying out demagnetizing and screening to obtain a pre-lithiated silicon-oxygen composite negative electrode material; the organic carbon source is one or a mixture of several of methane, ethylene, acetylene or benzene.
The following examples are given for the purpose of illustration.
Example 1
(1) Mixing materials:
mixing SiOxAdding lithium hydride and coal-series asphalt into a mechanical fusion machine according to the mass ratio of 100:0.5:0.5 for treatment for 5min, wherein x is 0.4, D50 is 2-5 mu m, and the softening point of the coal-series asphalt is 50-200 ℃; and obtaining the precursor of the silicon-oxygen composite negative electrode material.
(2) Block making:
and (2) putting the precursor of the silicon-oxygen composite negative electrode material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 150MPa, so that an isostatic pressing block is obtained.
(3) Primary carbonization:
and (3) putting the isostatic block obtained in the step (2) into a nitrogen atmosphere protection furnace for primary carbonization, raising the temperature to 800 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 4 hours, and mechanically crushing until D50 is 3-8 μm to obtain the primary carbonized silicon-oxygen composite negative electrode material.
(4) And (3) secondary carbonization:
and (4) placing the primarily carbonized silica composite negative electrode material obtained in the step (3) in an atmosphere furnace filled with methane for secondary carbonization, raising the temperature to 800 ℃ at a heating rate of 10 ℃/min, preserving the temperature for 3 hours, and removing magnetism and screening to obtain the pre-lithiated silica composite negative electrode material.
Example 2
(1) Mixing materials:
will SiOxAdding alkyl lithium and oil-based asphalt into a mechanical fusion machine according to the mass ratio of 100:10:5 for treatment for 20min, wherein x is 0.2, D50 is 2-5 mu m, and the softening point of the oil-based asphalt is 50-200 ℃; and obtaining the precursor of the silicon-oxygen composite negative electrode material.
(2) Block making:
and (2) putting the precursor of the silicon-oxygen composite negative electrode material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 100MPa, so that an isostatic pressing block is obtained.
(3) Primary carbonization:
and (3) putting the isostatic block obtained in the step (2) into a nitrogen atmosphere protection furnace for primary carbonization, raising the temperature to 400 ℃ at a heating rate of 25 ℃/min, preserving the temperature for 10 hours, and mechanically crushing until D50 is 3-8 mu m to obtain the primary carbonized silicon-oxygen composite negative electrode material.
(4) Secondary carbonization:
and (4) placing the primarily carbonized silica composite negative electrode material obtained in the step (3) in an atmosphere furnace filled with methane for secondary carbonization, raising the temperature to 600 ℃ at a heating rate of 30 ℃/min, preserving the temperature for 5 hours, and removing magnetism and screening to obtain the pre-lithiated silica composite negative electrode material.
Example 3
(1) Mixing materials:
mixing SiOxAdding lithium hydride and coal-series asphalt into a mechanical fusion machine according to the mass ratio of 100:5:3 for treatment for 10min, wherein x is 1, D50 is 2-5 mu m, and the softening point of the coal-series asphalt is 50-200 ℃; and obtaining the precursor of the silicon-oxygen composite negative electrode material.
(2) Block making:
and (2) putting the silica composite anode material precursor obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 200MPa, so as to obtain an isostatic pressing block.
(3) Primary carbonization:
and (3) putting the isostatic block obtained in the step (2) into a nitrogen atmosphere protection furnace for primary carbonization, raising the temperature to 8000 ℃ at a heating rate of 15 ℃/min, preserving the temperature for 8 hours, and mechanically crushing until D50 is 3-8 μm to obtain the primary carbonized silicon-oxygen composite negative electrode material.
(4) Secondary carbonization:
and (4) placing the primarily carbonized silica composite negative electrode material obtained in the step (3) in an atmosphere furnace filled with methane for secondary carbonization, raising the temperature to 900 ℃ at a heating rate of 20 ℃/min, preserving the temperature for 1 hour, and removing magnetism and screening to obtain the pre-lithiated silica composite negative electrode material.
Example 4
(1) Mixing materials:
mixing SiOxAdding lithium hydride and oil-based asphalt into a mechanical fusion machine according to the mass ratio of 100:8:1 for treatment for 17min, wherein x is 1.2, D50 is 2-5 mu m, and the softening point of the oil-based asphalt is 50-200 ℃; and obtaining the precursor of the silicon-oxygen composite negative electrode material.
(2) Block making:
and (2) putting the precursor of the silicon-oxygen composite negative electrode material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 250MPa, so that an isostatic pressing block is obtained.
(3) Primary carbonization:
and (3) putting the isostatic block obtained in the step (2) into a nitrogen atmosphere protection furnace for primary carbonization, raising the temperature to 1000 ℃ at a heating rate of 20 ℃/min, preserving the temperature for 7 hours, and mechanically crushing until D50 is 3-8 mu m to obtain the primary carbonized silicon-oxygen composite negative electrode material.
(4) Secondary carbonization:
and (4) placing the primarily carbonized silica composite negative electrode material obtained in the step (3) into an atmosphere furnace filled with methane for secondary carbonization, raising the temperature to 800 ℃ at a heating rate of 15 ℃/min, preserving the temperature for 3.5 hours, and removing magnetism and screening to obtain the pre-lithiated silica composite negative electrode material.
Example 5
(1) Mixing materials:
mixing SiOxAdding lithium hydride and coal-series asphalt into a mechanical fusion machine according to the mass ratio of 100:10:4.8 for treating for 8min, wherein x is 1.8, D50 is 2-5 mu m, and the softening point of the coal-series asphalt is 50-200 ℃; and obtaining the precursor of the silicon-oxygen composite negative electrode material.
(2) Block making:
and (2) putting the precursor of the silicon-oxygen composite negative electrode material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 180MPa, so that an isostatic pressing block is obtained.
(3) Primary carbonization:
and (3) putting the isostatic block obtained in the step (2) into a nitrogen atmosphere protection furnace for primary carbonization, raising the temperature to 850 ℃ at the heating rate of 23 ℃/min, preserving the temperature for 8.5 hours, and mechanically crushing until D50 is 3-8 mu m to obtain the primary carbonized silicon-oxygen composite negative electrode material.
(4) Secondary carbonization:
and (4) placing the silicon-oxygen composite negative electrode material subjected to the primary carbonization obtained in the step (3) into an atmosphere furnace filled with methane for secondary carbonization, raising the temperature to 675 ℃ at the heating rate of 13 ℃/min, preserving the temperature for 4.5 hours, and removing magnetism and screening to obtain the pre-lithiated silicon-oxygen composite negative electrode material.
Example 6
(1) Mixing materials:
mixing SiOxAdding lithium hydride and oil-based asphalt into a mechanical fusion machine according to the mass ratio of 100:2:3 for treatment for 13min, wherein x is 1.6, D50 is 2-5 mu m, and the softening point of the oil-based asphalt is 50-200 ℃; and obtaining the precursor of the silicon-oxygen composite negative electrode material.
(2) Block making:
and (2) putting the precursor of the silicon-oxygen composite negative electrode material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 100-300MPa, so as to obtain an isostatic pressed block.
(3) Primary carbonization:
and (3) putting the isostatic block obtained in the step (2) into a nitrogen atmosphere protection furnace for primary carbonization, raising the temperature to 450 ℃ at the heating rate of 12 ℃/min, preserving the temperature for 7.5 hours, and mechanically crushing until D50 is 3-8 μm to obtain the primary carbonized silicon-oxygen composite negative electrode material.
(4) And (3) secondary carbonization:
and (4) placing the primarily carbonized silica composite negative electrode material obtained in the step (3) into an atmosphere furnace filled with methane for secondary carbonization, raising the temperature to 650 ℃ at the heating rate of 12 ℃/min, preserving the temperature for 4.5 hours, and removing magnetism and screening to obtain the pre-lithiated silica composite negative electrode material.
Comparative example
Comparative example 1 is a prelithiated silicon oxygen composite anode material lacking step (2) and step (4), the other steps being the same as in example 1.
Comparative example 2 is a prelithiated silicon oxygen composite anode material lacking step (2), the other steps being the same as in example 1.
Comparative example 3 is a prelithiated silicon oxygen composite anode material lacking step (4), the other steps being the same as in example 1.
Performance test
The pre-lithiated silicon-oxygen composite anode materials prepared in the comparative examples and the examples were subjected to performance tests, and the test performances are shown in table 1 below.
TABLE 1
As can be seen from Table 1, the pre-lithiated silicon-oxygen composite negative electrode material prepared by the preparation method disclosed by the invention has excellent capacity performance, cycle performance and first charge-discharge efficiency. The double-layer compact and uniform coating layer plays a very critical role, the possibility of contact between the pre-lithiated silica composite material and a binder is reduced, and the performance of each aspect is improved.
Test method
And (3) electrochemical performance testing: in order to test the performance of the pre-lithiated silica composite negative electrode material, the pre-lithiated silica composite negative electrode material of the present invention was tested by a half-cell test method, and the negative electrode material of the above examples and comparative examples, SBR (solid content 50%), CMC: Super-p (weight ratio) 75: 6.5: 3.5: 15, was mixed with an appropriate amount of deionized water to form a slurry, was processed to evaluate the processability, was coated on a copper foil and dried in a vacuum drying oven for 12 hours to prepare a negative electrode sheet, the electrolyte was 1M LiPF6/EC + DEC + DMC 1: 1, the polypropylene microporous membrane was a separator, and the counter electrode was a lithium sheet, and a cell was assembled. And performing a constant-current charge and discharge experiment in the LAND battery test system, limiting the charge and discharge voltage to be 0.01-3.0V, and collecting and controlling data by using a charge and discharge cabinet controlled by a computer.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (6)
1. A preparation method of a pre-lithiated silica composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing materials:
adding silicon oxide, a reducing lithium-containing compound and a binder into a mechanical fusion machine according to a certain proportion, and treating for 5-20min to obtain a precursor of the silica composite negative electrode material;
(2) block making:
putting the precursor of the silicon-oxygen composite negative electrode material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 100-300MPa, so as to obtain an isostatic block;
(3) primary carbonization:
putting the isostatic block obtained in the step (2) into a nitrogen atmosphere protective furnace for primary carbonization, raising the temperature to 400-1000 ℃ at the heating rate of 2-25 ℃/min, preserving the heat for 4-10 hours, and mechanically crushing until D50=3-8 μm to obtain a silicon-oxygen composite negative electrode material subjected to primary carbonization;
(4) secondary carbonization:
and (4) placing the primarily carbonized silica composite negative electrode material obtained in the step (3) in an atmosphere furnace filled with an organic carbon source for secondary carbonization, raising the temperature to 600-900 ℃ at the heating rate of 10-30 ℃/min, preserving the temperature for 1-5 hours, and carrying out demagnetizing and screening to obtain the pre-lithiated silica composite negative electrode material.
2. The method of preparing a pre-lithiated silicone-oxygen composite material of claim 1, wherein: the silicon oxide in the step (1) is SiOxWherein 0 < x < 2, D50=2-5 μm.
3. The method of preparing a pre-lithiated silicone-oxygen composite material of claim 1, wherein: the reducing lithium-containing compound in the step (1) is one or a mixture of lithium hydride, alkyl lithium, metal lithium, lithium aluminum hydride and lithium amide.
4. The method of preparing a pre-lithiated silicone-oxygen composite material of claim 1, wherein: the binder in the step (1) is one or a mixture of two of coal-series asphalt and oil-series asphalt, and the softening point of the binder is 50-200 ℃.
5. The method of preparing a prelithiated silicon oxygen composite material of claim 1, wherein: the mass ratio of the silicon oxide, the reducing lithium-containing compound and the binding agent in the step (1) is 100 (0.5-10) to (0.5-5).
6. The method of preparing a prelithiated silicon oxygen composite material of claim 1, wherein: the organic carbon source in the step (4) is one or a mixture of several of methane, ethylene, acetylene or benzene.
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Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11185757A (en) * | 1997-12-17 | 1999-07-09 | Toyo Tanso Kk | Negative electrode material for lithium-ion secondary battery, manufacture thereof and lithium-ion secondary battery using the material |
| CN102593434A (en) * | 2011-01-11 | 2012-07-18 | 上海杉杉科技有限公司 | Composite graphite particles for lithium secondary battery and preparation method thereof |
| CN104577085A (en) * | 2014-12-17 | 2015-04-29 | 李震祺 | Lithium ion battery SiO negative electrode material and preparation method thereof |
| CN106025219A (en) * | 2016-06-24 | 2016-10-12 | 中天储能科技有限公司 | Spherical silicon-oxygen-carbon negative electrode composite material and preparation method and application thereof |
| CN108054351A (en) * | 2017-11-20 | 2018-05-18 | 海城申合科技有限公司 | A kind of lithium ion battery, silicon-carbon cathode material used and preparation method thereof |
| CN110416544A (en) * | 2019-06-06 | 2019-11-05 | 湖南中科星城石墨有限公司 | The method that half closed pore catalyzed graphitization of block prepares high capacity artificial plumbago negative pole material |
| CN110600720A (en) * | 2019-09-20 | 2019-12-20 | 广东省稀有金属研究所 | Composite silicon-based material, negative electrode material, preparation methods of composite silicon-based material and negative electrode material, and lithium ion battery |
| KR20190142177A (en) * | 2018-06-15 | 2019-12-26 | 주식회사 테라테크노스 | Method to manufacture silicon oxide cathode material of lithium battery |
| CN110649234A (en) * | 2019-08-21 | 2020-01-03 | 合肥国轩高科动力能源有限公司 | Preparation method of silicon-based negative electrode material with high coulombic efficiency |
| CN111106351A (en) * | 2019-12-30 | 2020-05-05 | 深圳市研一新材料有限责任公司 | Negative electrode lithium supplement additive and preparation method thereof |
| CN111725504A (en) * | 2020-05-26 | 2020-09-29 | 深圳市翔丰华科技股份有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN112164779A (en) * | 2020-09-24 | 2021-01-01 | 长沙矿冶研究院有限责任公司 | Carbon-coated silicon-based negative electrode material and preparation method thereof |
| CN112751027A (en) * | 2019-10-30 | 2021-05-04 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
| KR20210094623A (en) * | 2019-10-30 | 2021-07-29 | 비티알 뉴 머티리얼 그룹 코., 엘티디. | Silicon-oxygen composite anode material, manufacturing method thereof, and lithium ion battery |
| CN113184827A (en) * | 2021-04-27 | 2021-07-30 | 昆山宝创新能源科技有限公司 | Hard carbon cathode composite material and preparation method and application thereof |
| CN113363479A (en) * | 2021-03-31 | 2021-09-07 | 万向一二三股份公司 | Double-layer carbon-coated silicon oxide negative electrode material and preparation method and application thereof |
| CN113422029A (en) * | 2021-06-29 | 2021-09-21 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
| US20210296633A1 (en) * | 2020-03-20 | 2021-09-23 | GM Global Technology Operations LLC | Methods of briquetting precursor materials for prelithiated silicon active materials |
| US20210384500A1 (en) * | 2019-05-28 | 2021-12-09 | Btr New Material Group Co., Ltd. | Silicon oxide/carbon composite negative electrode material and preparation method therefor, and lithium-ion battery |
| WO2022001880A1 (en) * | 2020-06-28 | 2022-01-06 | 贝特瑞新材料集团股份有限公司 | Silicon-oxygen composite negative electrode material, negative electrode, lithium ion battery and preparation method therefor |
| CN113948688A (en) * | 2021-09-30 | 2022-01-18 | 浙江锂宸新材料科技有限公司 | Modified pre-lithiated silica composite material and preparation method and application thereof |
-
2022
- 2022-02-25 CN CN202210177732.2A patent/CN114744166A/en active Pending
Patent Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11185757A (en) * | 1997-12-17 | 1999-07-09 | Toyo Tanso Kk | Negative electrode material for lithium-ion secondary battery, manufacture thereof and lithium-ion secondary battery using the material |
| CN102593434A (en) * | 2011-01-11 | 2012-07-18 | 上海杉杉科技有限公司 | Composite graphite particles for lithium secondary battery and preparation method thereof |
| CN104577085A (en) * | 2014-12-17 | 2015-04-29 | 李震祺 | Lithium ion battery SiO negative electrode material and preparation method thereof |
| CN106025219A (en) * | 2016-06-24 | 2016-10-12 | 中天储能科技有限公司 | Spherical silicon-oxygen-carbon negative electrode composite material and preparation method and application thereof |
| CN108054351A (en) * | 2017-11-20 | 2018-05-18 | 海城申合科技有限公司 | A kind of lithium ion battery, silicon-carbon cathode material used and preparation method thereof |
| KR20190142177A (en) * | 2018-06-15 | 2019-12-26 | 주식회사 테라테크노스 | Method to manufacture silicon oxide cathode material of lithium battery |
| US20210384500A1 (en) * | 2019-05-28 | 2021-12-09 | Btr New Material Group Co., Ltd. | Silicon oxide/carbon composite negative electrode material and preparation method therefor, and lithium-ion battery |
| CN110416544A (en) * | 2019-06-06 | 2019-11-05 | 湖南中科星城石墨有限公司 | The method that half closed pore catalyzed graphitization of block prepares high capacity artificial plumbago negative pole material |
| CN110649234A (en) * | 2019-08-21 | 2020-01-03 | 合肥国轩高科动力能源有限公司 | Preparation method of silicon-based negative electrode material with high coulombic efficiency |
| CN110600720A (en) * | 2019-09-20 | 2019-12-20 | 广东省稀有金属研究所 | Composite silicon-based material, negative electrode material, preparation methods of composite silicon-based material and negative electrode material, and lithium ion battery |
| CN112751027A (en) * | 2019-10-30 | 2021-05-04 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
| KR20210094623A (en) * | 2019-10-30 | 2021-07-29 | 비티알 뉴 머티리얼 그룹 코., 엘티디. | Silicon-oxygen composite anode material, manufacturing method thereof, and lithium ion battery |
| CN111106351A (en) * | 2019-12-30 | 2020-05-05 | 深圳市研一新材料有限责任公司 | Negative electrode lithium supplement additive and preparation method thereof |
| US20210296633A1 (en) * | 2020-03-20 | 2021-09-23 | GM Global Technology Operations LLC | Methods of briquetting precursor materials for prelithiated silicon active materials |
| CN111725504A (en) * | 2020-05-26 | 2020-09-29 | 深圳市翔丰华科技股份有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| WO2021238600A1 (en) * | 2020-05-26 | 2021-12-02 | 深圳市翔丰华科技股份有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method therefor |
| WO2022001880A1 (en) * | 2020-06-28 | 2022-01-06 | 贝特瑞新材料集团股份有限公司 | Silicon-oxygen composite negative electrode material, negative electrode, lithium ion battery and preparation method therefor |
| CN112164779A (en) * | 2020-09-24 | 2021-01-01 | 长沙矿冶研究院有限责任公司 | Carbon-coated silicon-based negative electrode material and preparation method thereof |
| CN113363479A (en) * | 2021-03-31 | 2021-09-07 | 万向一二三股份公司 | Double-layer carbon-coated silicon oxide negative electrode material and preparation method and application thereof |
| CN113184827A (en) * | 2021-04-27 | 2021-07-30 | 昆山宝创新能源科技有限公司 | Hard carbon cathode composite material and preparation method and application thereof |
| CN113422029A (en) * | 2021-06-29 | 2021-09-21 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
| CN113948688A (en) * | 2021-09-30 | 2022-01-18 | 浙江锂宸新材料科技有限公司 | Modified pre-lithiated silica composite material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 张刚;刘兴稳;张帆;陈至炜: "高首效长寿命硅碳复合材料的制备及其电化学性能", 储能科学与技术, vol. 9, no. 003 * |
| 王金莹;曲江英;李杰兰;汤占磊;臧云浩;王涛;顾建峰;周钢;高峰;: "二次包覆法制备煤沥青基硅/碳复合物及其锂离子电池性能", 应用化学, no. 05 * |
| 贺劲鑫;郑媛媛;靳承铀;缪永华;: "锂电池硅基负极材料制备及性能表征", 电源技术, no. 04 * |
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