CN111900365A - Silicon-based negative electrode material and preparation method and application thereof - Google Patents
Silicon-based negative electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111900365A CN111900365A CN202010922747.8A CN202010922747A CN111900365A CN 111900365 A CN111900365 A CN 111900365A CN 202010922747 A CN202010922747 A CN 202010922747A CN 111900365 A CN111900365 A CN 111900365A
- Authority
- CN
- China
- Prior art keywords
- silicon
- negative electrode
- electrode material
- based negative
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a silicon-based negative electrode material and a preparation method and application thereof. The invention provides a silicon-based negative electrode material, which comprises a silicon material and a polymer coated on the surface of the silicon material. According to the silicon-based negative electrode material provided by the invention, the polymer coated on the surface of the silicon material can better conduct lithium ions, so that the defect of low first charge-discharge efficiency of the silicon material is overcome; meanwhile, the polyphosphazenes polymer has high elasticity, can well buffer stress caused by volume change of a silicon material, and ensures that an SEI film cannot crack, so that the cycle performance of the lithium ion battery is improved; in addition, the polyphosphazene polymer also has certain flame retardant property, so that the safety performance of the lithium ion battery can be effectively improved, and therefore, the silicon-based negative electrode material provided by the invention can effectively improve the first charge-discharge efficiency, the cycle performance and the safety performance of the lithium ion battery.
Description
Technical Field
The invention relates to a silicon-based negative electrode material, a preparation method and application thereof, and relates to the technical field of lithium ion batteries.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, environmental friendliness and the like, so the lithium ion battery is widely applied. At present, graphite is used as the most commonly used negative electrode material in the lithium ion battery, the theoretical specific capacity of the graphite is 372mAh/g, so that the development of the lithium ion battery towards higher energy density is limited, the theoretical specific capacity of the silicon material can reach 4200mAh/g, and when the graphite is replaced by the graphite to be used as the negative electrode material of the lithium ion battery, the energy density of the lithium ion battery can be remarkably improved, and the graphite is a next-generation negative electrode material with a good application prospect.
However, the silicon material undergoes a large volume change in the process of lithium deintercalation, so that the SEI film on the surface of the negative electrode material is continuously cracked and regrown, resulting in low first charge-discharge efficiency and poor cycle performance of the lithium ion battery. Therefore, more and more attention is paid to how to improve the performance of the silicon material, thereby improving the first charge-discharge efficiency and the cycle life of the lithium ion battery.
Disclosure of Invention
The invention provides a silicon-based negative electrode material and a preparation method thereof, which are used for solving the problems of low first charge-discharge efficiency and poor cycle performance of a lithium ion battery caused by volume change of a silicon material.
The invention provides a silicon-based negative electrode material, which comprises a silicon material and a polymer coated on the surface of the silicon material, wherein the polymer has a structure shown in a formula 1,
wherein n is more than or equal to 5 and less than or equal to 50000, R1、R2Independently selected from-Cl, -F, -Br, alkyl, fluoroalkyl, alkoxy, fluoroalkoxy and-NHCeH2e+1，e≥1、-NCfH2f+1CgH2g+1，f≥1，g≥1、-CpH2p-7，p≥6、-OCqH2q-7，q≥6、-CkH2k-7-zFz，k≥6，1≤z≤2k-7、-OCmH2m-7-uFu，m≥6，1≤u≤2m-7、-O(CH2CH2O)hR0，h≥0、-O(CF2CF2O)iR0，i≥0、-O(CH2CH2O)jCOCR0＝CH2，j≥0、-(CH2CH2O)rCOCR0＝CH2，r≥0、-OC6H4(CH2CH2O)sR0S is not less than 0;
R0is one of H, alkyl, fluoroalkyl, phenyl and fluorophenyl.
The alkyl group of the present invention is represented by the general formula-CnH2n+1A straight-chain or branched saturated hydrocarbon radical of, for example, -CH3、-CH2CH3、-CH2CH2CH3Etc.; fluoroalkyl refers to a radical of the formula-CnH2n+1-xFx(1. ltoreq. x. ltoreq.2 n +1) saturated hydrocarbon radicals substituted by one or more fluorine, e.g. -CH2F、-CH2CF3、-CH2CF2CF3Etc.; alkoxy means a radical of the formula-OCnH2n+1Saturated hydrocarbon radicals containing oxygen atoms, e.g. -OCH3、-OCH2CH3Etc.; fluoroalkoxy means a radical of the formula-OCnH2n+1-xFx(1. ltoreq. x. ltoreq.2 n +1) alkoxy substituted by one or more fluorine, e.g. -OCF3、-OCH2CF2CF3Etc.; phenyl means a structure of-C6H5A group having a benzene ring as a functional group; by fluorophenyl is meant phenyl substituted by one or more fluorine groups, e.g. -C6H4F、C6H3F2And the like.
The invention provides a silicon-based negative electrode material which comprises a silicon material and a polymer coated on the surface of the silicon material, wherein the polymer is a polyphosphazene polymer with a structure shown in formula 1, the main chain of the polymer is formed by alternately arranging single bonds and double bonds of phosphorus and nitrogen, and each phosphorus atom is connected with two side groups R1And R2，R1And R2May be a halogen or an organic group, the selection of the particular pendant group being as described above. According to the silicon-based negative electrode material provided by the invention, the polymer coated on the surface of the silicon material can better conduct lithium ions, so that the defect of low first charge-discharge efficiency of the silicon material is overcome; meanwhile, the polyphosphazenes polymer has high elasticity, can still maintain good mechanical strength and elasticity even under the soaking of electrolyte, can well buffer the stress caused by the volume change of the silicon material, and ensures that an SEI film cannot be broken, thereby improving the cycle performance of the lithium ion battery; in addition, because the polyphosphazene polymer also has certain flame retardant property, the safety performance of the lithium ion battery can be effectively improved; therefore, the silicon-based negative electrode material provided by the invention can effectively improve the first charge-discharge efficiency, the cycle performance and the safety performance of the lithium ion battery.
In one embodiment, R may be further modified to further improve the performance of the lithium ion battery1、R2Is selected, in particular R1、R2Each independently selected from-Cl, alkoxy, fluoroalkoxy and-NCfH2f+1CgH2g+1，f≥1，g≥1、-O(CH2CH2O)hR0，h≥0、-O(CF2CF2O)iR0，i≥0、-CpH2p-7，p≥6、-O(CH2CH2O)jCOCR0＝CH2And j is not less than 0.
Further, R1、R2Each independently selected from-Cl, -OCH2CH3、-OCH2CF2CF3、-NC2H5C2H5、-CH2C6H5、-O(CH2CH2O)4CH3、-O(CF2CF2O)4CH3、-O(CH2CH2O)10COC(CH3)＝CH2One kind of (1).
The applicant researches and discovers that the performance of the lithium ion battery is gradually improved along with the gradual improvement of the quality of the polymer, but the cycle performance of the lithium ion battery is reduced on the contrary when the quality of the polymer is too high, so that the quality of the polymer needs to be controlled, and particularly, the quality of the polymer is 0.01-5% of the total mass of the silicon-based negative electrode material.
The silicon material in the silicon-based negative electrode material can be selected according to the prior art, and specifically, the silicon material is one or more of silicon oxide, carbon-coated silicon oxide, silicon, carbon-coated silicon and a silicon-carbon composite material.
The applicant researches and discovers that the grain size and shape of the silicon material have a large influence on the performance of the lithium ion battery, so that a person skilled in the art can select the corresponding silicon material according to the prior art and actual preparation needs, and particularly, the average grain size of the silicon material is 5nm-20 μm.
The shape of the silicon material is one of regular or irregular granular shape, sheet shape, linear shape, rod shape, hollow spherical shape, tubular shape and porous granular shape.
In conclusion, the silicon-based negative electrode material provided by the invention effectively improves the first charge-discharge efficiency, the cycle performance and the safety performance of the lithium ion battery by coating the surface of the silicon material with the polyphosphazene polymer.
The second aspect of the invention provides a preparation method of any one of the silicon-based anode materials, which comprises the following steps:
and mixing the cyclotriphosphazene monomer with a silicon material, heating under vacuum to enable the cyclotriphosphazene monomer to perform polymerization reaction, and obtaining the silicon-based negative electrode material after the reaction is finished.
The invention provides a preparation method of a silicon-based negative electrode material, which comprises the steps of firstly, selecting a proper cyclotriphosphazene monomer and a proper silicon material, dissolving the proper cyclotriphosphazene monomer and the proper silicon material in a solvent, uniformly mixing, and evaporating the solvent to dryness; and secondly, heating the evaporated material under a vacuum condition to enable cyclotriphosphazene monomer to perform polymerization reaction to obtain polyphosphazene, fully washing with a solvent after the polymerization reaction is finished, and removing the solvent to obtain the silicon-based negative electrode material. According to the preparation method of the silicon-based negative electrode material, the surface of the silicon material is coated with the polyphosphazene polymer, and the polymer can better conduct lithium ions, so that the defect of low first charge-discharge efficiency of the silicon material is overcome; meanwhile, the polyphosphazenes polymer has high elasticity, can still maintain good mechanical strength and elasticity even under the soaking of electrolyte, can well buffer the stress caused by the volume change of the silicon material, and ensures that an SEI film cannot be broken, thereby improving the cycle performance of the lithium ion battery; in addition, the polyphosphazene polymer also has certain flame retardant property, so that the safety performance of the lithium ion battery can be effectively improved, and therefore, the silicon-based negative electrode material provided by the invention can effectively improve the first charge-discharge efficiency, the cycle performance and the safety performance of the lithium ion battery.
In a specific embodiment, the cyclotriphosphazene monomer is one of hexachlorocyclotriphosphazene, hexafluorocyclotriphosphazene and hexabromocyclotriphosphazene; the silicon material is selected as described above.
Firstly, dissolving a cyclotriphosphazene monomer and a silicon material in a solvent, uniformly mixing, and evaporating the solvent to dryness to obtain a mixture of the cyclotriphosphazene monomer and the silicon material;
specifically, the solvent is one or more of petroleum ether, n-hexane, cyclohexane, n-heptane, benzene, toluene and xylene, and the skilled person can select the corresponding solvent according to the actual preparation requirement.
And secondly, heating the mixture under a vacuum condition to enable cyclotriphosphazene monomers to perform polymerization reaction to obtain polyphosphazene, fully washing with a solvent after the polymerization reaction is finished, and removing the solvent to obtain the silicon-based negative electrode material.
Specifically, when the above monomer compound is used, the resulting polymer pendant group R is prepared1And R2respectively-Cl, -F and-Br; if a polymer containing other side chains needs to be obtained, the polymer can be further reacted with a nucleophilic reagent on the basis of the preparation method to obtain the silicon-based negative electrode material.
For example, when R is1And/or R2is-OCH2CH3In this case, CH can be added under the protection of protective gas based on the above preparation method3CH2ONa is reacted to obtain R1And/or R2is-OCH2CH3And finally washing and removing the solvent to obtain the silicon-based negative electrode material.
In conclusion, the invention provides the preparation method of the silicon-based anode material, which is simple, easy to operate and suitable for large-scale production.
The invention provides a lithium ion battery, which comprises any one of the silicon-based negative electrode materials.
The third aspect of the invention provides a lithium ion battery, wherein a negative plate is prepared on the basis of the silicon-based negative electrode material provided by the invention, and the lithium ion battery is prepared by matching a positive plate, a diaphragm and electrolyte according to a conventional process. In the process of preparing the negative plate, the silicon-based negative material and graphite are mixed as the negative active material in consideration of the comprehensive performance of the lithium ion battery, for example, the silicon-based negative material, the graphite, the conductive agent, the binder and the solvent provided by the invention are fully and uniformly mixed to prepare negative slurry, the negative slurry is coated on the surface of a negative current collector, and the negative plate is obtained after drying and rolling. The preparation can be carried out by a person skilled in the art according to the prior art and in combination with actual preparation requirements, a suitable negative electrode slurry material is selected, and the proportion of the silicon-based negative electrode material and the graphite negative electrode material is adjusted. The lithium ion battery provided by the invention has good first charge-discharge efficiency, cycle performance and safety performance.
The implementation of the invention has at least the following advantages:
1. according to the silicon-based negative electrode material provided by the invention, the polymer coated on the surface of the silicon material can better conduct lithium ions, so that the defect of low first charge-discharge efficiency of the silicon material is overcome; meanwhile, the polyphosphazenes polymer has high elasticity, can still maintain good mechanical strength and elasticity even under the soaking of electrolyte, can well buffer the stress caused by the volume change of the silicon material, and ensures that an SEI film cannot be broken, thereby improving the cycle performance of the lithium ion battery; in addition, the polyphosphazene polymer also has certain flame retardant property, so that the safety performance of the lithium ion battery can be effectively improved, and therefore, the silicon-based negative electrode material provided by the invention can effectively improve the first charge-discharge efficiency, the cycle performance and the safety performance of the lithium ion battery.
2. The lithium ion battery provided by the invention has good first charge-discharge efficiency, cycle performance and safety performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The silicon materials used in the following examples were purchased from Shenzhen beibeite New energy materials GmbH, and hexachlorocyclotriphosphazene was purchased from Shanghai Aladdin Biotechnology GmbH.
Example 1
The silicon-based negative electrode material provided by the embodiment comprises silicon oxide and a polymer coated on the surface of the silicon oxide, wherein the silicon oxide is in an irregular granular shape, and the Dv50 of the silicon oxide is 20 microns; the polymer has a structure shown in formula 1, the average polymerization degree n is 1000, and R1And R2Are all-Cl, and the mass of the polymer is 0.01 percent of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based anode material provided by the embodiment comprises the following steps:
dissolving 0.02 mass part of hexachlorocyclotriphosphazene and 100 mass parts of silicon monoxide in 200 mass parts of toluene, fully stirring for 4h by using a mechanical stirrer, uniformly mixing, evaporating the solvent, heating for 48h at 200 ℃ in vacuum (vacuum degree of 10Pa), washing the obtained material by using toluene after the reaction is finished, filtering to remove the solvent, and drying at 150 ℃ to obtain the silicon-based negative electrode material.
The preparation method of the negative electrode plate provided by the embodiment comprises the following steps:
fully and uniformly mixing 20 parts by mass of a silicon-based negative electrode material, 74 parts by mass of a graphite negative electrode material, 2.0 parts by mass of conductive agent carbon black, 1.0 part by mass of conductive agent carbon nano tube, 2.5 parts by mass of binder SBR, 0.5 part by mass of carboxymethyl cellulose and 100 parts by mass of water to prepare negative electrode slurry, coating the negative electrode slurry on the surface of a 6-micron copper foil, drying at 110 ℃, rolling under 40 tons of pressure, and compacting the density of 1.72g/cm3Obtaining the negative plate, wherein the surface density of the negative plate is 8.1mg/cm3。
Example 2
The silicon-based negative electrode material provided by the embodiment comprises silicon oxide and a polymer coated on the surface of the silicon oxide, wherein the silicon oxide is in an irregular granular shape, and the Dv50 of the silicon oxide is 20 microns; the polymer has a structure shown in formula 1, the average polymerization degree n is 1000, and R1And R2Are all-Cl, and the mass of the polymer is 0.11 percent of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based negative electrode material and the negative electrode sheet provided in this example can refer to example 1, and the difference is that the mass part of hexachlorocyclotriphosphazene is 0.21.
Example 3
The silicon-based negative electrode material provided by the embodiment comprises silicon oxide and a polymer coated on the surface of the silicon oxide, wherein the silicon oxide is in an irregular granular shape, and the Dv50 of the silicon oxide is 20 microns; the polymer has a structure shown in formula 1, the average polymerization degree n is 1000, and R1And R2The mass of the polymer is 1.31 percent of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based negative electrode material and the negative electrode sheet provided by this embodiment can refer to embodiment 1, and the difference is that the mass part of hexachlorocyclotriphosphazene is 2.01.
Example 4
The silicon-based negative electrode material provided by the embodiment comprises silicon oxide and a polymer coated on the surface of the silicon oxide, wherein the silicon oxide is in an irregular granular shape, and the Dv50 of the silicon oxide is 20 microns; the polymer has a structure shown in formula 1, the average polymerization degree n is 1000, and R1And R2The mass of the polymer is 4.99 percent of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based negative electrode material and the negative electrode sheet provided in this example can refer to example 1, and the difference is that the mass part of hexachlorocyclotriphosphazene is 7.06.
Example 5
The silicon-based negative electrode material provided by the embodiment comprises silicon oxide and a polymer coated on the surface of the silicon oxide, wherein the silicon oxide is in an irregular granular shape, and the Dv50 of the silicon oxide is 20 microns; the polymer has a structure shown in formula 1, the average polymerization degree n is 1000, and R1And R2Are all-Cl, and the mass of the polymer is 7.75 percent of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based negative electrode material and the negative electrode sheet provided by this example can refer to example 1, and the difference is that the mass part of hexachlorocyclotriphosphazene is 10.38.
Comparative example 1
The silicon-based negative electrode material provided by the comparative example is silica which is in irregular particle shape, and the Dv50 of the silicon-based negative electrode material is 20 microns;
the preparation method of the negative electrode sheet provided by the comparative example is the same as that of example 1.
Example 6
The silicon-based negative electrode material provided by the embodiment comprises a silicon material and a polymer coated on the surface of the silicon material, wherein the silicon material is carbon-coated silicon monoxide, the carbon-coated silicon monoxide is in an irregular granular shape, and the Dv50 of the silicon-based negative electrode material is 10 micrometers;the polymer has a structure shown in formula 1, the average polymerization degree n is 800, and R1And R2The mass of the polymer is 1.29 percent of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based negative electrode material provided in this example can refer to example 1, and the difference is that the mass portion of hexachlorocyclotriphosphazene is 2.16, the silicon material is carbon-coated silica with a thickness of 10 μm, the polymerization temperature is 250 ℃, and the reaction time is 24 hours.
The method for preparing the negative electrode sheet provided in this example may be referred to example 1, except that the compacted density is 1.70g/cm3The surface density of the negative plate is 8.4mg/cm3。
Comparative example 2
The silicon-based negative electrode material provided by the comparative example is carbon-coated silica, the carbon-coated silica is irregular particles, and the Dv50 of the silicon-based negative electrode material is 10 micrometers;
the preparation method of the negative electrode sheet provided by the comparative example is the same as that of example 6.
Example 7
The silicon-based negative electrode material provided by the embodiment comprises silicon and a polymer coated on the surface of the silicon, wherein the silicon is a regular spherical particle, and the Dv50 of the silicon is 5 nm; the polymer has a structure shown in formula 1, the average polymerization degree n is 400, and R1And R2Are all-Cl, and the mass of the polymer is 1.67 percent of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based negative electrode material provided in this example can refer to example 1, and the difference is that the mass portion of hexachlorocyclotriphosphazene is 2.52, the silicon material is 5nm silicon, the polymerization temperature is 300 ℃, and the reaction time is 12 hours.
The negative electrode sheet provided in this example was prepared by referring to example 1 except that the compacted density was 1.63g/cm3The surface density of the negative plate is 4.9mg/cm3。
Comparative example 3
The silicon-based negative electrode material provided by the comparative example is silicon, the silicon is spherical particles, and the Dv50 of the silicon-based negative electrode material is 5 nm;
the preparation method of the negative electrode sheet provided by the comparative example is the same as that of example 7.
Example 8
The silicon-based negative electrode material provided by the embodiment comprises a silicon material and a polymer coated on the surface of the silicon material, wherein the silicon material is carbon-coated silicon, the carbon-coated silicon is linear, and Dv50 of the silicon-based negative electrode material is 100 nm; the polymer has a structure shown in formula 1, the average polymerization degree n is 400, and R1And R2Are all-Cl, and the mass of the polymer is 1.35 percent of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based negative electrode material provided in this example can refer to example 1, and the difference is that the mass portion of hexachlorocyclotriphosphazene is 3.24, the silicon material is 100nm carbon-coated silicon, the polymerization temperature is 350 ℃, and the reaction time is 2 hours.
The negative electrode sheet provided in this example was prepared by referring to example 1 except that the compacted density was 1.59g/cm3The surface density of the negative plate is 5.3mg/cm3。
Comparative example 4
The silicon-based negative electrode material provided by the comparative example is carbon-coated silicon, the carbon-coated silicon is linear, and the Dv50 is 100 nm;
the preparation method of the negative electrode sheet provided by the comparative example is the same as that of example 8.
Example 9
The silicon-based negative electrode material provided by the embodiment comprises silicon oxide and a polymer coated on the surface of the silicon oxide, wherein the silicon oxide is in an irregular granular shape, and the Dv50 of the silicon oxide is 8 microns; the polymer has a structure shown in formula 1, the average polymerization degree n is 30000, R1And R2Are all-O (CH)2CH2O)4CH3The mass of the polymer is 3.08 percent of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based anode material provided by the embodiment comprises the following steps:
dissolving 3 parts by mass of hexachlorocyclotriphosphazene and 100 parts by mass of silica material in 150 parts by mass of petroleum ether, fully stirring for 8 hours by using a mechanical stirrer, uniformly mixing, evaporating the solvent, heating for 25 hours at 270 ℃ in vacuum (vacuum degree of 8Pa), washing the obtained material by using the petroleum ether after the reaction is finished, and filtering to remove the solventDrying at 60 ℃; then, under the protection of nitrogen, it was added to a volume of 200mL containing 0.25mol/L of CH3(OCH2CH2)4Stirring and refluxing ONa in tetrahydrofuran solution at 65 ℃, reacting for 48h, cooling to room temperature, evaporating the solvent, washing with water and petroleum ether in sequence, filtering to remove the solvent, and drying at 60 ℃ to obtain the silicon-based negative electrode material.
The method for preparing the negative electrode sheet provided in this example may be referred to example 1, except that the compacted density is 1.69g/cm3The surface density of the negative plate is 8.0mg/cm3。
Example 10
The silicon-based negative electrode material provided by the embodiment comprises silicon oxide and a polymer coated on the surface of the silicon oxide, wherein the silicon oxide is in an irregular granular shape, and the Dv50 of the silicon oxide is 8 microns; the polymer has a structure shown in formula 1, the average polymerization degree n is 50000, R1And R2Are all-OCH2CH3The mass of the polymer is 1.58% of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based anode material provided by this example can refer to example 9, and the difference is that the polymerization temperature is 230 ℃, the reaction time is 48 hours, and the nucleophilic reagent contains 0.25mol/L CH3CH2Ethanol solution of ONa.
The preparation method of the negative electrode sheet provided in this example is the same as that of example 9.
Example 11
The silicon-based negative electrode material provided by the embodiment comprises silicon oxide and a polymer coated on the surface of the silicon oxide, wherein the silicon oxide is in an irregular granular shape, and the Dv50 of the silicon oxide is 8 microns; the polymer has a structure shown in formula 1, the average polymerization degree n is 500, and R1And R2Are all-OCH2CF2CF3The mass of the polymer is 1.86 percent of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based negative electrode material provided in this example can refer to example 9, and the difference is that the polymerization temperature is 290 ℃, the reaction time is 6 hours, and the nucleophile contains 0.25mol/LCF3CF2CH2II of ONaAnd (3) an oxygen hexacyclic ring solution.
The preparation method of the negative electrode sheet provided in this example is the same as that of example 9.
Example 12
The silicon-based negative electrode material provided by the embodiment comprises silicon oxide and a polymer coated on the surface of the silicon oxide, wherein the silicon oxide is in an irregular granular shape, and the Dv50 of the silicon oxide is 8 microns; the polymer has a structure shown in formula 1, the average polymerization degree n is 5, R1And R2Are all-O (CF)2CF2O)4CH3The mass of the polymer is 2.14% of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based anode material provided in this example can refer to example 9, and the difference is that the polymerization temperature is 340 ℃, the reaction time is 0.5h, and the nucleophile contains 0.25mol/L CH3(OCF2CF2)4Tetrahydrofuran solution of ONa.
The preparation method of the negative electrode sheet provided in this example is the same as that of example 9.
Example 13
The silicon-based negative electrode material provided by the embodiment comprises silicon oxide and a polymer coated on the surface of the silicon oxide, wherein the silicon oxide is in an irregular granular shape, and the Dv50 of the silicon oxide is 8 microns; the polymer has a structure shown in formula 1, the average polymerization degree n is 300, and R1And R2Are all-O (CH)2CH2O)10COC(CH3)＝CH2The mass of the polymer is 6.29 percent of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based anode material provided by this example can refer to example 9, and the difference is that the polymerization temperature is 250 ℃, the reaction time is 18h, and the nucleophilic reagent contains 0.25mol/L NaO (CH)2CH2O)10COC(CH3)＝CH2The glycol dimethyl ether solution of (1).
The preparation method of the negative electrode sheet provided in this example is the same as that of example 9.
Example 14
The silicon-based negative electrode material provided by the embodiment comprises silicon monoxide and silicon dioxide coated with the silicon monoxideA polymer of the surface, wherein the silica is irregularly granular with a Dv50 of 8 μm; the polymer has a structure shown in formula 1, the average polymerization degree n is 300, and R1is-O (CH)2CH2O)10COC(CH3)＝CH2，R2is-Cl; the mass of the polymer is 3.15% of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based negative electrode material and the negative electrode sheet provided by the embodiment can refer to embodiment 13, and is different from that the concentration of the nucleophile is 0.125 mol/L.
Example 15
The silicon-based negative electrode material provided by the embodiment comprises silicon oxide and a polymer coated on the surface of the silicon oxide, wherein the silicon oxide is in an irregular granular shape, and the Dv50 of the silicon oxide is 8 microns; the polymer has a structure shown in formula 1, the average polymerization degree n is 300, and R1And R2Are all-NC2H5C2H5The mass of the polymer is 2.33 percent of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based negative electrode material and the negative electrode sheet provided in this example can refer to example 13, and the difference is that the nucleophile is 0.25mol/L HNC2H5C2H5A triethylamine solution of (2).
Example 16
The silicon-based negative electrode material provided by the embodiment comprises silicon oxide and a polymer coated on the surface of the silicon oxide, wherein the silicon oxide is in an irregular granular shape, and the Dv50 of the silicon oxide is 8 microns; the polymer has a structure shown in formula 1, the average polymerization degree n is 300, and R1is-CH2C6H5，R2is-O (CF)2CF2O)4CH3The mass of the polymer is 1.99 percent of the total mass of the silicon-based negative electrode material.
The preparation method of the silicon-based negative electrode material provided in this example can refer to example 13, and the difference is that there are two kinds of nucleophiles, namely, 0.125mol/L C is firstly contained6H5CH2MgBr in tetrahydrofuran (Grignard reagent) and reacted with a solution containing 0.125mol/L of CH3(OCF2CF2)4And reacting ONa in tetrahydrofuran solution.
The preparation method of the negative electrode sheet provided in this example is the same as that of example 13.
Comparative example 5
The silicon-based negative electrode material provided by the comparative example is silicon oxide, the silicon oxide is in irregular particles, and the Dv50 is 8 mu m;
the preparation method of the negative electrode sheet provided by the comparative example is the same as that of example 9.
Example 17
The silicon-based negative electrode material provided by the embodiment is the same as that in the embodiment 1;
the preparation method of the negative electrode sheet provided in this example can refer to example 1, and is different in that the negative electrode slurry includes 40 parts by mass of the silicon-based negative electrode material and 54 parts by mass of the graphite negative electrode material, and the compaction density is 1.61g/cm3The surface density of the negative plate is 5.9mg/cm3。
Comparative example 6
The silicon-based negative electrode material provided by the comparative example is silicon oxide, the silicon oxide is irregular particles, and the Dv50 of the silicon-based negative electrode material is 20 microns;
the preparation method of the negative electrode sheet provided by the comparative example is the same as that of example 17.
Example 18
The silicon-based negative electrode material provided by the embodiment is the same as that in the embodiment 1;
the preparation method of the negative electrode sheet provided in this example can refer to example 1, and is different in that the negative electrode slurry includes 94 parts by mass of the silicon-based negative electrode material and 0 part by mass of the graphite negative electrode material, and the compaction density is 1.44g/cm3The surface density of the negative plate is 4.1mg/cm3。
Comparative example 7
The silicon-based negative electrode material provided by the comparative example is silicon oxide, the silicon oxide is irregular particles, and the Dv50 of the silicon-based negative electrode material is 20 microns;
the preparation method of the negative electrode sheet provided by the comparative example is the same as that of example 18.
The lithium ion battery is prepared by further matching the negative electrode sheets provided in examples 1 to 18 and comparative examples 1 to 7 with the positive electrode sheet, the diaphragm and the electrolyte, and the first charge-discharge efficiency, the first cycle performance and the first safety performance of the lithium ion battery are tested, and the test results are shown in table 1:
the preparation method of the lithium ion battery comprises the following steps: the lithium ion battery is prepared by matching the negative plate with a positive plate, a Polyethylene (PE) porous diaphragm (a wet diaphragm ND12 produced by Shanghai Enjie New Material science and technology Co., Ltd., thickness of 12 μm) and an electrolyte (an electrolyte of type LBC445B33 produced by Shenzhen New Zealand science and technology Co., Ltd.).
The preparation method of the positive plate comprises the following steps: 97 parts by mass of lithium cobaltate (4.4V lithium cobaltate from Hu south China fir energy science and technology Co., Ltd.), 1.5 parts by mass of conductive agent carbon black, 1.5 parts by mass of binder PVDF and 50 parts by mass of solvent NMP are fully and uniformly mixed to prepare lithium cobaltate anode slurry, the slurry is coated on the surface of an aluminum foil with the thickness of 10 mu m, then the aluminum foil is dried at the temperature of 120 ℃ and rolled under the pressure of 40 tons, and the compaction density is 4.15g/cm3Obtaining the positive plate with the surface density of 18mg/cm2。
The method for testing the first charge-discharge efficiency comprises the following steps:
the electrochemical performance tester of the lithium ion battery is used for testing, and a charging and discharging system is set as follows: charging to 4.4V at constant current of 0.2C, charging at constant voltage until the current is less than 0.01C, and recording the first charge capacity QCharging deviceStanding for 5 minutes, discharging the lithium ion battery to the final voltage of 3.0V at a constant current of 0.2C, and recording the first discharge capacity QPutFirst charge-discharge efficiency η ═ QPut/QCharging device*100％。
The cycle performance testing method comprises the following steps:
the cycle performance of the lithium ion battery is tested by referring to the GB/T18287-2013 standard, wherein the cycle test conditions are as follows: at 25 ℃ and 0.5C/0.5C (the upper limit voltage was set to 4.4V, and the lower limit voltage was set to 3.0V).
The safety performance testing method comprises the following steps:
the safety performance of the lithium ion battery is tested by referring to the GB/T31485-.
Table 1 results of performance testing of lithium ion batteries provided in examples 1-18 and comparative examples 1-7
As can be seen from table 1, the first charge efficiency, cycle life and safety performance of the lithium ion batteries prepared on the basis of the negative electrode sheets provided in examples 1 to 18 are all higher than those of comparative examples 1 to 7, and it can be seen from the data provided in examples 1 to 5 that as the quality of the polymer is continuously improved, the performance of the lithium ion batteries is gradually improved, but when the quality of the polymer exceeds 5%, the cycle life of the lithium ion batteries is obviously reduced; according to the data provided in examples 9 to 16, it can be seen that the difference in the influence of the specific structure of the polymer on the performance of the lithium ion battery is small, and therefore, the performance of the lithium ion battery can be effectively improved by the silicon-based negative electrode material provided by the invention.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A silicon-based negative electrode material is characterized by comprising a silicon material and a polymer coated on the surface of the silicon material, wherein the polymer has a structure shown in a formula 1,
wherein n is more than or equal to 5 and less than or equal to 50000, R1、R2Are respectively and independently selected from-Cl, -F, -Br,Alkyl, fluoroalkyl, alkoxy, fluoroalkoxy, -NHCeH2e+1，e≥1、-NCfH2f+1CgH2g+1，f≥1，g≥1、-CpH2p-7，p≥6、-OCqH2q-7，q≥6、-CkH2k-7- zFz，k≥6，1≤z≤2k-7、-OCmH2m-7-uFu，m≥6，1≤u≤2m-7、-O(CH2CH2O)hR0，h≥0、-O(CF2CF2O)iR0，i≥0、-O(CH2CH2O)jCOCR0＝CH2，j≥0、-(CH2CH2O)rCOCR0＝CH2，r≥0、-OC6H4(CH2CH2O)sR0S is not less than 0;
R0is one of H, alkyl, fluoroalkyl, phenyl and fluorophenyl.
2. The silicon-based anode material of claim 1, wherein R is1、R2Each independently selected from-Cl, alkoxy, fluoroalkoxy and-NCfH2f+1CgH2g+1，f≥1，g≥1、-O(CH2CH2O)hR0，h≥0、-O(CF2CF2O)iR0，i≥0、-CpH2p-7，p≥6、-O(CH2CH2O)jCOCR0＝CH2And j is not less than 0.
3. The silicon-based anode material of claim 1, wherein R is1、R2Each independently selected from-Cl, -OCH2CH3、-OCH2CF2CF3、-NC2H5C2H5、-CH2C6H5、-O(CH2CH2O)4CH3、-O(CF2CF2O)4CH3、-O(CH2CH2O)10COC(CH3)＝CH2One kind of (1).
4. Silicon-based anode material according to any of claims 1 to 3, characterized in that the mass of the polymer is 0.01 to 5% of the total mass of the silicon-based anode material.
5. The silicon-based anode material as claimed in any one of claims 1 to 4, wherein the silicon material is one or more of silicon oxide, carbon-coated silicon oxide, silicon, carbon-coated silicon, and silicon-carbon composite material.
6. The silicon-based anode material according to any one of claims 1 to 5, wherein the silicon material has an average particle size of 5nm to 20 μm.
7. The silicon-based negative electrode material as claimed in claim 5, wherein the shape of the silicon material is one of regular or irregular granular shape, flake shape, linear shape, rod shape, hollow spherical shape, tubular shape, and porous granular shape.
8. A preparation method of the silicon-based anode material as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
and mixing the cyclotriphosphazene monomer with a silicon material, heating under vacuum to enable the cyclotriphosphazene monomer to perform polymerization reaction, and obtaining the silicon-based negative electrode material after the reaction is finished.
9. The method of claim 8, wherein the cyclotriphosphazene monomer is one of hexachlorocyclotriphosphazene, hexafluorocyclotriphosphazene and hexabromocyclotriphosphazene.
10. A lithium ion battery comprising the silicon-based negative electrode material according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010922747.8A CN111900365A (en) | 2020-09-04 | 2020-09-04 | Silicon-based negative electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010922747.8A CN111900365A (en) | 2020-09-04 | 2020-09-04 | Silicon-based negative electrode material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111900365A true CN111900365A (en) | 2020-11-06 |
Family
ID=73225084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010922747.8A Pending CN111900365A (en) | 2020-09-04 | 2020-09-04 | Silicon-based negative electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111900365A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022133440A1 (en) * | 2020-12-14 | 2022-06-23 | Global Graphene Group, Inc. | Lithium-protecting polymer composite layer for a lithium metal secondary battery and manufacturing method |
| WO2022170334A1 (en) * | 2021-02-03 | 2022-08-11 | Global Graphene Group, Inc. | Phosphazene compound-based elastic polymer-encapsulated anode particles for lithium batteries and method of manufacturing |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104812485A (en) * | 2012-11-19 | 2015-07-29 | 弗劳恩霍弗应用技术研究院 | Particulate electrode material having coating made of crystalline inorganic material and/or inorganic-organic hybrid polymer and method for production thereof |
| CN108630919A (en) * | 2018-04-04 | 2018-10-09 | 合肥国轩高科动力能源有限公司 | A kind of carbon coating silicon/graphene complex and its preparation method and application |
| CN109286012A (en) * | 2018-09-29 | 2019-01-29 | 北京科技大学 | A kind of high magnification aoxidizes the preparation method of sub- silicon substrate lithium cell negative pole material |
| CN109411713A (en) * | 2018-09-10 | 2019-03-01 | 江苏塔菲尔新能源科技股份有限公司 | The machinery of the modified composite material of siliceous substrates material is total to method for coating, modified composite material and lithium ion battery |
| CN109970981A (en) * | 2017-12-27 | 2019-07-05 | 华为技术有限公司 | A kind of solid fireproof polymer, electrode slice, diaphragm and lithium secondary battery |
| CN110402508A (en) * | 2017-02-16 | 2019-11-01 | 纳米技术仪器公司 | The method that manufacture has the lithium secondary battery of shielded high capacity active material of positive electrode |
| WO2020154235A1 (en) * | 2019-01-22 | 2020-07-30 | Xg Sciences, Inc. | Silicon/graphene composite anode material and method to manufacture the same |
-
2020
- 2020-09-04 CN CN202010922747.8A patent/CN111900365A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104812485A (en) * | 2012-11-19 | 2015-07-29 | 弗劳恩霍弗应用技术研究院 | Particulate electrode material having coating made of crystalline inorganic material and/or inorganic-organic hybrid polymer and method for production thereof |
| CN110402508A (en) * | 2017-02-16 | 2019-11-01 | 纳米技术仪器公司 | The method that manufacture has the lithium secondary battery of shielded high capacity active material of positive electrode |
| CN109970981A (en) * | 2017-12-27 | 2019-07-05 | 华为技术有限公司 | A kind of solid fireproof polymer, electrode slice, diaphragm and lithium secondary battery |
| CN108630919A (en) * | 2018-04-04 | 2018-10-09 | 合肥国轩高科动力能源有限公司 | A kind of carbon coating silicon/graphene complex and its preparation method and application |
| CN109411713A (en) * | 2018-09-10 | 2019-03-01 | 江苏塔菲尔新能源科技股份有限公司 | The machinery of the modified composite material of siliceous substrates material is total to method for coating, modified composite material and lithium ion battery |
| CN109286012A (en) * | 2018-09-29 | 2019-01-29 | 北京科技大学 | A kind of high magnification aoxidizes the preparation method of sub- silicon substrate lithium cell negative pole material |
| WO2020154235A1 (en) * | 2019-01-22 | 2020-07-30 | Xg Sciences, Inc. | Silicon/graphene composite anode material and method to manufacture the same |
Non-Patent Citations (2)
| Title |
|---|
| 吴少军: "聚磷腈的多功能化和应用研究", 《中国硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 罗文君 等: "《大分子设计与试验》", 30 September 2012, 中国地质大学出版社有限责任公司 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022133440A1 (en) * | 2020-12-14 | 2022-06-23 | Global Graphene Group, Inc. | Lithium-protecting polymer composite layer for a lithium metal secondary battery and manufacturing method |
| WO2022170334A1 (en) * | 2021-02-03 | 2022-08-11 | Global Graphene Group, Inc. | Phosphazene compound-based elastic polymer-encapsulated anode particles for lithium batteries and method of manufacturing |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110148708B (en) | Negative plate and lithium ion battery | |
| CN110739485A (en) | low-temperature lithium ion batteries | |
| CN106531963B (en) | Lithium ion battery cathode slurry and lithium ion battery | |
| KR20180115813A (en) | Binder for lithium cell, composition for producing electrode, and electrode | |
| CN113113605B (en) | Network structure ion conductive adhesive and preparation method and application thereof | |
| CN113410468B (en) | Negative electrode binder and preparation method thereof, preparation method of negative electrode sheet and lithium ion battery | |
| CN111900365A (en) | Silicon-based negative electrode material and preparation method and application thereof | |
| CN109904454B (en) | Silicon-containing polymer binder, preparation method thereof and application thereof in silicon-based electrode lithium ion battery | |
| CN103915609A (en) | Silicon-silicon oxide-carbon composite material, lithium ion secondary battery anode material, preparation methods of two and application of composite material | |
| CN111244454A (en) | High-proportion silicon cathode water system composite binder and application thereof | |
| CN112447971B (en) | Positive electrode material additive, active material, positive electrode material, preparation of positive electrode material and application of positive electrode material in lithium ion battery | |
| CN110128650B (en) | Conductive polymer binder and preparation method and application thereof | |
| CN113980629A (en) | Binder and lithium ion battery containing same | |
| US20210057725A1 (en) | Slurry composition for lithium ion secondary battery and electrode for lithium ion secondary battery | |
| US20200411871A1 (en) | Binder composition for non-aqueous secondary battery electrode, conductive material paste composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode, electrode for non-aqueous secondary battery, and non-aqueous secondary battery | |
| JP2021518472A (en) | Polyamide-imide binder for lithium-ion batteries | |
| CN111029541A (en) | Silicon-carbon composite electrode material for honeycomb-like lithium ion battery and preparation method thereof | |
| CN113299919B (en) | Positive pole piece and lithium ion battery comprising same | |
| CN114335546B (en) | Binder for battery electrode and battery electrode | |
| CN113764673B (en) | Electrode paste composition, method of preparing the same, electrode sheet coated with the same, and lithium ion battery including the electrode sheet | |
| CN113321199B (en) | Polybenzoxazine-co-cresol-based polymer-derived hard carbon microspheres, and preparation method and application thereof | |
| US11673984B2 (en) | Binder composition for non-aqueous secondary battery electrode, conductive material paste composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode, electrode for non-aqueous secondary battery, and non-aqueous secondary battery | |
| US20240030442A1 (en) | Binder composition for electrode of non-aqueous lithium ion secondary battery and method of producing the same, binder solution for electrode of non-aqueous lithium ion secondary battery, slurry composition for electrode of non-aqueous lithium ion secondary battery, electrode for non-aqueous lithium ion secondary battery, and non-aqueous lithium ion secondary battery | |
| CN113054182B (en) | Graft copolymer coated silicon-based material and preparation method thereof | |
| EP3771002A1 (en) | Secondary battery binder composition, secondary battery electrode conductive paste, secondary battery electrode slurry composition, method for producing secondary battery electrode slurry composition, secondary battery electrode, and secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201106 |