CN111634918A - Lithium ion battery cathode material and low-cost preparation method thereof - Google Patents
Lithium ion battery cathode material and low-cost preparation method thereof Download PDFInfo
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- CN111634918A CN111634918A CN202010526244.9A CN202010526244A CN111634918A CN 111634918 A CN111634918 A CN 111634918A CN 202010526244 A CN202010526244 A CN 202010526244A CN 111634918 A CN111634918 A CN 111634918A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 39
- 239000010406 cathode material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000003345 natural gas Substances 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000007773 negative electrode material Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 15
- 229910052814 silicon oxide Inorganic materials 0.000 description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910021423 nanocrystalline silicon Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
-
- 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 lithium ion battery cathode material and a low-cost preparation method thereof, wherein the low-cost preparation method of the lithium ion battery cathode material comprises the following steps: heating the silicon monoxide powder in a rotary calcining furnace to 900-1200 ℃ in a high-purity nitrogen atmosphere, preserving heat for 0.5-1 h, introducing a mixed gas of high-purity nitrogen and natural gas to perform carbon coating on the silicon monoxide powder in overturning, and finally performing crushing and grading treatment to obtain the lithium ion battery cathode material. The preparation method is simple, suitable for continuous and large-scale production and low in production cost, and the button cell prepared from the lithium ion battery cathode material has high initial capacity, high initial efficiency and high 50-week capacity retention rate.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a lithium ion battery cathode material and a low-cost preparation method thereof.
Background
Currently, environmental pollution of all countries around the world is becoming serious, new energy automobiles replace fuel automobiles to be used as effective measures for solving the problem of environmental pollution, the new energy automobiles are widely concerned and developed to the utmost, and lithium ion batteries are used as energy supply parts of the new energy automobiles, so that the problems of improving energy density, increasing endurance energy and reducing production cost are urgently needed to be solved. In addition, with the development of economy, the demand for low-cost high-capacity lithium ion batteries is increasing.
The silicon oxide negative electrode material is widely concerned and researched due to the ultrahigh specific capacity and excellent cycle performance, is the negative electrode material which is most probably popularized and applied to electric automobiles and 5G mobile equipment at present, but the development of market application of the silicon oxide negative electrode material is limited due to the higher production cost of the silicon oxide negative electrode material, for example, Chinese patent with the publication number of CN1302075C discloses a conductive silicon compound, the preparation of the conductive silicon compound and the negative electrode material of a non-aqueous electrolyte secondary battery, the silicon oxide negative electrode material is prepared by coating gas phase deposition carbon of methane, ethane, ethylene, acetylene and the like, all gas cost of the silicon oxide negative electrode material is higher, so that the integral manufacturing cost of the negative electrode material is higher, and the silicon oxide negative electrode material is not suitable for the requirement of large-scale popularization; chinese patent publication No. CN106532009A discloses a method for preparing a hard carbon composite negative electrode material for a high-capacity lithium ion battery, in which asphalt and resin are used for solid phase coating, and the carbon layer coated by the method is not uniform, the product quality uniformity and stability are poor, continuous production cannot be realized, and the production cost is high; chinese patent publication No. CN1032022446A discloses a silicon oxide/carbon negative electrode material for lithium ion batteries and a preparation method thereof, wherein resin, pitch and the like are dissolved in an organic solvent for liquid phase coating, the procedure is complex, large-scale production is difficult to realize, and the production cost is high.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the lithium ion battery cathode material and the low-cost preparation method thereof.
In order to achieve the purpose, the invention adopts the specific scheme that:
the low-cost preparation method of the lithium ion battery cathode material comprises the following steps: heating the silicon monoxide powder in a rotary calcining furnace to 900-1200 ℃ in a high-purity nitrogen atmosphere, preserving heat for 0.5-1 h, introducing a mixed gas of high-purity nitrogen and natural gas to perform carbon coating on the silicon monoxide powder in overturning, and finally performing crushing and grading treatment to obtain the lithium ion battery cathode material.
Further, the silica powder was placed in a rotary calciner, and high-purity nitrogen gas was introduced into the rotary calciner to perform atmosphere replacement until the oxygen content in the rotary calciner became less than 50ppm, followed by heating. The process atmosphere must be kept out of air to the maximum extent possible, in particular out of oxygen and moisture in the air, to ensure that the material is not oxidized during the production process. The adoption of high-purity nitrogen can ensure that the material cannot be oxidized, and further ensure the capacity and the first effect of the prepared cathode material.
Further, the median particle diameter D50 of the silica powder is not greater than 8 μm. The reason for limiting the particle size of the silicon oxide powder is to prevent the material from having large internal resistance and severe expansion due to the excessive particle size of the silicon oxide powder, and further to prevent the service life of the lithium battery from being influenced.
Further, the heating rate during heating is 3-10 ℃/min.
Further, the ratio of high-purity nitrogen to natural gas in the mixed gas is 100: (3-50).
A lithium ion battery cathode material is prepared by the method.
Has the advantages that:
1. when the lithium ion battery cathode material is prepared, the material is heated at high temperature and mixed with the mixed gas of high-purity nitrogen and natural gas, so that on one hand, the organizational structure of the material is changed, an organizational structure which takes the silicon monoxide as a matrix and disperses the nano-silicon dioxide and the nano-crystalline silicon in the silicon monoxide matrix is formed, the structure can ensure higher capacity and first effect, and can ensure longer cycle life; on the other hand, the natural gas decomposes carbon at high temperature to deposit on the surface of the material, so as to improve the conductivity of the material, reduce the contact between the electrolyte and the silicon substrate and further improve the first effect and the cycle life of the material. And finally, removing particles with overlarge particle sizes in the material by crushing, so that the uniformity of the particle size of the material is ensured, and the uniformity of the material is further ensured.
2. The preparation method is simple, the air source is easy to obtain, the button cell is suitable for continuous and large-scale production, the production cost is low, the first capacity and the first efficiency of the button cell prepared by the lithium ion battery cathode material are high, and the 50-week capacity retention rate is high.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, belong to the scope of the present invention.
The low-cost preparation method of the lithium ion battery cathode material comprises the following steps: firstly, putting the silicon monoxide powder with the median particle size D50 not more than 8 mu m into a rotary calcining furnace, introducing high-purity nitrogen into the rotary calcining furnace for atmosphere replacement until the oxygen content in the furnace is lower than 50ppm, then heating to 900-1200 ℃ at the heating rate of 3-10 ℃/min, preserving heat for 0.5-1 h, then introducing the high-purity nitrogen and natural gas according to the ratio of 100: and (3) carrying out carbon coating on the silica powder in the overturning process by using the mixed gas mixed according to the proportion of (3-50), and finally carrying out crushing and grading treatment to obtain the lithium ion battery cathode material.
A lithium ion battery cathode material is prepared by the method.
The raw materials and gases used in the present invention: the particle size D50 of the silicon oxide powder is less than or equal to 8 mu m; high-purity nitrogen with the purity more than or equal to 99.99 percent; natural gas, municipal gas supply; the above raw materials are all conventional commercially available products, and the present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
The low-cost preparation method of the lithium ion battery cathode material comprises the following steps: placing the silicon monoxide powder with the granularity D50 being 7.8 mu m into a rotary calcining furnace, then using high-purity nitrogen to perform atmosphere replacement in the rotary calcining furnace until the oxygen content in the furnace reaches below 50ppm, heating to 900 ℃ at the heating rate of 3 ℃/min and preserving heat for 0.5h, then introducing mixed gas of the high-purity nitrogen and natural gas, wherein the ratio of the high-purity nitrogen to the natural gas is 100: and 3, opening a rotary valve of the rotary calcining furnace, performing carbon coating on the turned-over silicon monoxide powder, and finally performing crushing and grading treatment to obtain the lithium ion battery cathode material.
Example 2
The low-cost preparation method of the lithium ion battery cathode material comprises the following steps: placing the silicon monoxide powder with the granularity D50 being 6.2 mu m into a rotary calcining furnace, then using high-purity nitrogen to perform atmosphere replacement in the rotary calcining furnace until the oxygen content in the furnace reaches below 50ppm, heating to 1000 ℃ at the heating rate of 5 ℃/min, preserving heat for 1h, then introducing mixed gas of the high-purity nitrogen and natural gas, wherein the ratio of the high-purity nitrogen to the natural gas is 100: and 20, opening a rotary valve of the rotary calcining furnace, performing carbon coating on the turned-over silicon monoxide powder, and finally performing crushing and grading treatment to obtain the lithium ion battery cathode material.
Example 3
The low-cost preparation method of the lithium ion battery cathode material comprises the following steps: placing the silicon monoxide powder with the granularity D50 being 5.1 mu m into a rotary calcining furnace, then using high-purity nitrogen to perform atmosphere replacement in the rotary calcining furnace until the oxygen content in the furnace reaches below 50ppm, heating to 1200 ℃ at the heating rate of 10 ℃/min, preserving heat for 1h, then introducing mixed gas of the high-purity nitrogen and natural gas, wherein the ratio of the high-purity nitrogen to the natural gas is 100: and 50, opening a rotary valve of the rotary calcining furnace, performing carbon coating on the turned-over silicon monoxide powder, and finally performing crushing and grading treatment to obtain the lithium ion battery cathode material.
Comparative example
The preparation method of the lithium ion battery cathode material comprises the following steps: placing silicon monoxide powder with the particle size D50 being 5.1 mu m into a rotary calcining furnace, then using high-purity nitrogen to perform atmosphere replacement in the rotary calcining furnace until the oxygen content in the furnace reaches below 50ppm, heating to 1000 ℃ at the heating rate of 5 ℃/min, preserving heat for 1h, then introducing mixed gas of the high-purity nitrogen and acetylene, wherein the ratio of the high-purity nitrogen to the acetylene is 100: and 20, opening a rotary valve of the rotary calcining furnace, performing carbon coating on the turned-over silicon monoxide powder, and finally performing crushing and grading treatment to obtain the lithium ion battery cathode material.
Effects of the embodiment
The characterization method of the material comprises the following steps: (1) the first capacity and the first efficiency test of the material are characterized by using a button cell, and the charge-discharge multiplying power of the lithium-ion battery is 0.1C and the charge-discharge voltage range is 0.005V-1.5V when the motor is a metal lithium sheet; (2) the cycle performance of the material is characterized by using a button cell mixed with graphite, and the material and the graphite are as follows: after graphite is mixed according to the mass ratio of 1:9, coating a copper foil to prepare a pole piece, and assembling the button cell by taking a metal lithium piece as a counter electrode; (3) and the 50-week capacity retention ratio is the ratio of the 50-week charge capacity to the 1-week charge capacity. The performance parameters of examples 1-3 and comparative example are shown in table 1.
TABLE 1 Performance parameters of samples prepared in examples 1-3 and comparative examples
| First capacity (mAh/g) | First efficiency (%) | 50-week capacity retention (%) | |
| Example 1 | 1672 | 75.1 | 95 |
| Example 2 | 1653 | 76.2 | 97 |
| Example 3 | 1643 | 75.8 | 97 |
| Comparative example | 1650 | 76.1 | 96 |
As can be seen from table 1, the performance of the lithium ion battery cathode material prepared from the mixed gas of high-purity nitrogen and natural gas is substantially the same as that of the lithium ion battery cathode material prepared from the mixed gas of acetylene and high-purity nitrogen with higher cost, and therefore, the lithium ion battery cathode material prepared by the preparation method provided by the invention meets the use requirements.
The foregoing is merely a preferred embodiment of the invention and is not to be construed as limiting the invention in any way. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. The low-cost preparation method of the lithium ion battery cathode material is characterized by comprising the following steps of: heating the silicon monoxide powder in a rotary calcining furnace to 900-1200 ℃ in a high-purity nitrogen atmosphere, preserving heat for 0.5-1 h, introducing a mixed gas of high-purity nitrogen and natural gas to perform carbon coating on the silicon monoxide powder in overturning, and finally performing crushing and grading treatment to obtain the lithium ion battery cathode material.
2. The method of claim 1, wherein the silica powder is placed in a rotary calciner, high purity nitrogen is introduced into the rotary calciner to replace the atmosphere until the oxygen content in the rotary calciner is less than 50ppm, and then the rotary calciner is heated.
3. The low-cost preparation method of the lithium ion battery anode material according to claim 1, wherein the median particle size D50 of the silicon monoxide powder is not more than 8 μm.
4. The low-cost preparation method of the lithium ion battery negative electrode material according to claim 1, wherein the heating rate is 3-10 ℃/min.
5. The low-cost preparation method of the lithium ion battery anode material according to claim 1, wherein the ratio of high-purity nitrogen to natural gas in the mixed gas is 100: (3-50).
6. A lithium ion battery negative electrode material, characterized in that it is prepared by the method of claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113571678A (en) * | 2021-06-24 | 2021-10-29 | 惠州锂威新能源科技有限公司 | Preparation method of negative electrode material, product and application |
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| CN108550837A (en) * | 2018-06-04 | 2018-09-18 | 深圳市比克动力电池有限公司 | Lithium ion battery comprehensive silicon negative material and preparation method thereof |
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| CN110391409A (en) * | 2019-07-25 | 2019-10-29 | 昆山宝创新能源科技有限公司 | Lithium cell cathode material and preparation method thereof and lithium battery |
| CN110556529A (en) * | 2019-10-15 | 2019-12-10 | 溧阳天目先导电池材料科技有限公司 | Cathode composite material with multilayer core-shell structure and preparation method and application thereof |
| CN111082006A (en) * | 2019-12-06 | 2020-04-28 | 深圳市比克动力电池有限公司 | Silicon monoxide composite negative electrode material, preparation method thereof and lithium ion battery |
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| CN113571678A (en) * | 2021-06-24 | 2021-10-29 | 惠州锂威新能源科技有限公司 | Preparation method of negative electrode material, product and application |
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