CN113307272A - Lithium ion battery, silica negative electrode material, and preparation method and application thereof - Google Patents

Lithium ion battery, silica negative electrode material, and preparation method and application thereof Download PDF

Info

Publication number
CN113307272A
CN113307272A CN202110769147.7A CN202110769147A CN113307272A CN 113307272 A CN113307272 A CN 113307272A CN 202110769147 A CN202110769147 A CN 202110769147A CN 113307272 A CN113307272 A CN 113307272A
Authority
CN
China
Prior art keywords
silicon
conductive agent
oxygen
fluorine
negative electrode
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
Application number
CN202110769147.7A
Other languages
Chinese (zh)
Inventor
徐荣飞
李冰
刘朗
姜艳
梁世硕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kunshan Bao Innovative Energy Technology Co Ltd
Original Assignee
Kunshan Bao Innovative Energy Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kunshan Bao Innovative Energy Technology Co Ltd filed Critical Kunshan Bao Innovative Energy Technology Co Ltd
Priority to CN202110769147.7A priority Critical patent/CN113307272A/en
Publication of CN113307272A publication Critical patent/CN113307272A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/956—Silicon carbide
    • C01B32/963—Preparation from compounds containing silicon
    • 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
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/483—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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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 relates to a lithium ion battery, a silicon-oxygen cathode material, and a preparation method and application thereof. The preparation method of the silicon-oxygen anode material comprises the following steps: dispersing an organic fluorine-containing carbon source and a conductive agent in a solvent to obtain a dispersion liquid; then coating the surface of the silicon oxide compound, and drying; carrying out heat treatment under the protection of protective gas; wherein the silicon oxide has a ratio of the amount of silicon to oxygen species of 1: (0.85-1.2); the organic fluorine-containing carbon source is linear fluorine-containing polymer, and the conductive agent is a flaky conductive agent; or the organic fluorine-containing carbon source is a cross-linked fluorine-containing polymer, and the conductive agent is a granular conductive agent. By specifically selecting the combination of the linear fluorine-containing polymer and the flaky conductive agent or the combination of the cross-linked fluorine-containing polymer and the granular conductive agent, the silicon oxide negative electrode material has good coating capability, can form a good coating layer on the surface of the silicon oxide, and is modified to obtain the silicon oxide negative electrode material with good electrochemical performance.

Description

Lithium ion battery, silica negative electrode material, and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery, a silica negative electrode material, and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high open circuit voltage, large energy density, long service life, no memory effect, less pollution, small self-discharge rate and the like, is superior to other traditional secondary batteries in comprehensive performance, and is considered as the most ideal power supply for various portable electronic equipment and electric automobiles. Although the traditional lithium ion battery cathode material graphite has the advantages of good cycling stability, higher cost performance and the like, the traditional lithium ion battery cathode material graphite has no advantages due to lower charge-discharge specific capacity and volume specific capacity, and is difficult to meet the higher requirements of power systems, particularly electric vehicles and hybrid electric vehicles, on battery capacity.
Among many new cathode materials, simple substance materials such as silicon, tin, germanium, etc., metal oxides and composite metal oxide materials are attracting more and more attention due to their high theoretical lithium intercalation capacity. However, most of these high capacity enrichment materials have low conductivity and have severe volume effect under high degree of lithium deintercalation, resulting in poor cycling stability of the electrode. Taking silicon as an example, the volume expansion of silicon reaches up to 300% during charging, so that the powder particles are gradually pulverized and collapsed under a large mechanical action force, the loss of active materials is caused, and the cycle performance of the negative electrode is also seriously reduced.
At present, a carbon-coated silicon measure is generally adopted to improve the problems of charge volume expansion and conductivity of silicon materials. However, the traditional carbon coating means (graphite coating or organic carbon source coating) has poor coating property and poor stability of the silicon negative electrode material, and the electrochemical performance still cannot meet the actual use requirement.
Disclosure of Invention
Therefore, it is necessary to provide a silicon-oxygen anode material with good coating property and electrochemical performance, and a preparation method and an application thereof.
In addition, it is necessary to provide a lithium ion battery and a rechargeable product using the silicon-oxygen negative electrode material with good electrochemical performance.
In one aspect of the invention, a preparation method of a silicon-oxygen anode material is provided, which comprises the following steps:
dispersing an organic fluorine-containing carbon source and a conductive agent in a solvent to obtain a dispersion liquid, wherein the organic fluorine-containing carbon source is a linear fluorine-containing polymer, and the conductive agent is a flaky conductive agent, or the organic fluorine-containing carbon source is a crosslinked fluorine-containing polymer, and the conductive agent is a granular conductive agent;
mixing silicon oxide with the dispersion liquid, and drying to obtain mixed powder, wherein the mass ratio of silicon to oxygen of the silicon oxide is 1: (0.85-1.2);
and under the protection of protective gas, carrying out heat treatment on the mixed powder.
In some of these embodiments, the linear fluoropolymer is selected from at least one of polyvinylidene fluoride, polymerized tetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene copolymer, polychlorotrifluoroethylene, and tetrafluoroethylene-ethylene copolymer.
In some of these embodiments, the sheet-like conductive agent is selected from at least one of graphene, reduced graphene oxide, and graphene nanoribbons.
In some of these embodiments, the crosslinked fluoropolymer is selected from at least one of a nitroso-based fluoroelastomer, a fluorine-containing polyester-based fluoroelastomer, a fluorosilicone rubber, and a fluorine-containing polyacrylate fluoroelastomer.
In some of these embodiments, the particulate conductive agent is selected from at least one of conductive carbon black, ketjen black, and furnace black.
In some embodiments, the mass ratio of the organic fluorine-containing carbon source to the conductive agent to the silicon oxide is (12-20): 1: (95-105).
In some of these embodiments, the temperature of the heat treatment is 600 ℃ to 1200 ℃ and the time of the heat treatment is 1 hour to 6 hours.
On the other hand, the invention also provides a silicon-oxygen anode material which is obtained according to the preparation method of the silicon-oxygen anode material; the silica anode material comprises an inner core, a first shell layer and a second shell layer;
the first shell layer is wrapped on the surface of the inner core; the second shell layer is wrapped on the surface of the first shell layer;
the inner core is silicon oxide, and the mass ratio of silicon to oxygen in the silicon oxide is 1: (0.85-1.2); the first shell layer is made of silicon carbide; the second shell layer is a fluorine-containing carbon layer doped with a conductive agent.
In another aspect of the invention, the invention also provides a lithium ion battery, and the negative plate of the lithium ion battery contains the silica negative electrode material.
In another aspect of the present invention, a rechargeable product is provided, which contains the lithium ion battery.
According to the preparation method of the silicon-oxygen negative electrode material, the organic fluorine-containing carbon source and the conductive agent are prepared into the dispersion liquid, the dispersion liquid is coated on the surface of silicon oxide in a liquid phase coating mode, then drying and heat treatment are carried out, and the silicon-oxygen negative electrode material can be obtained, wherein the linear fluorine-containing polymer and the flaky conductive agent are specifically selected to be combined, or the cross-linked fluorine-containing polymer and the granular conductive agent are combined, so that the dispersion liquid has good coating capacity, a good coating layer can be formed on the surface of the silicon oxide, and the silicon oxide is modified to obtain the silicon-.
In addition, the preparation method of the silicon-oxygen cathode material is simple in process, and the prepared silicon-oxygen cathode material has good first charge efficiency and cycle stability and good electrochemical performance.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing a silicon-oxygen negative electrode material according to an embodiment of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing a silicon-oxygen negative electrode material, including the following steps S100 to S300.
Step S100: dispersing an organic fluorine-containing carbon source and a conductive agent in a solvent to obtain a dispersion liquid, wherein the organic fluorine-containing carbon source is a linear fluorine-containing polymer, and the conductive agent is a flaky conductive agent, or the organic fluorine-containing carbon source is a cross-linked fluorine-containing polymer, and the conductive agent is a granular conductive agent.
Step S200: silicon oxide (SiO)x) Mixing with the dispersion, and drying to obtain mixed powder, silicon oxide (SiO)x) The ratio of the amount of silicon to oxygen species of (a) is 1: (0.85-1.2).
Step S300: and carrying out heat treatment on the mixed powder under the protection of protective gas.
The organic fluorine-containing carbon source contains high-activity fluorine elements, so that the reactivity is strong. Under the heat treatment, the organic fluorine-containing carbon source can react with silicon oxide to generate silicon carbide on the surface of the silicon oxide on the one hand, and can also be pyrolyzed to form a fluorine-containing carbon layer to realize carbon coating on the silicon oxide on the other hand.
The preparation method of the silicon-oxygen cathode material comprises the steps of preparing organic fluorine-containing carbon source and conductive agent into dispersion, and coating silicon oxide (SiO) in a liquid phase coating modex) The surface is dried and thermally treated to obtain the silicon-oxygen negative electrode material, wherein the combination of linear fluorine-containing polymer and flaky conductive agent or the combination of cross-linked fluorine-containing polymer and granular conductive agent is specifically selected, so that the dispersion has good coating capability, a good coating layer can be formed on the surface of silicon oxide, and silicon oxide (SiO) can be coatedx) Modifying to obtain the silicon-oxygen cathode material with good electrochemical performance.
In addition, the preparation method of the silicon-oxygen cathode material is simple in process, and the prepared silicon-oxygen cathode material has good first charge efficiency and cycle stability and good electrochemical performance.
In some of these embodiments, the linear fluoropolymer is selected from at least one of polyvinylidene fluoride, polymerized tetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene copolymer, polychlorotrifluoroethylene, and tetrafluoroethylene-ethylene copolymer.
In some of these embodiments, the sheet-like conductive agent is selected from at least one of graphene, reduced graphene oxide, and graphene nanoribbons.
In some of these embodiments, the graphene sheets have a thickness of 1 to 10 layers, preferably 2 to 3 layers.
In some of these embodiments, the graphene has a sheet diameter of 1nm to 1000 nm, preferably 30 nm to 80 nm.
In some of these embodiments, the crosslinked fluoropolymer is selected from at least one of a nitroso-based fluoroelastomer, a fluorine-containing polyester-based fluoroelastomer, a fluorosilicone rubber, and a fluorine-containing polyacrylate fluoroelastomer.
In some of these embodiments, the particulate conductive agent is selected from at least one of conductive carbon black, ketjen black, and furnace black.
In some of these embodiments, the particulate conductive agent has a particle size of 1nm to 80 nm.
In some of these embodiments, silicon oxide (SiO)x) The ratio of the amount of silicon to oxygen species in the mixture is 1: (0.95-1.05).
In some of these embodiments, the solvent may be selected from water, C1-C6Alcohol, C3-C8At least one of ketone, N-methyl pyrrolidone, toluene and xylene.
In some embodiments, the mass ratio of the organic fluorine-containing carbon source, the conductive agent and the silicon oxide is (12-20): 1: (95-105).
In some embodiments, the mass ratio of the organic fluorine-containing carbon source to the solvent is (10-20): (80-90).
In some of these embodiments, step S100 includes:
step S110: mixing an organic fluorine-containing carbon source with a solvent to obtain a fluorine-containing carbon source solution;
step S120: and mixing the conductive agent with the fluorine-containing carbon source solution to obtain a dispersion liquid.
In some of these embodiments, the manner of drying in step S200 is spray drying.
In some embodiments, in step S300, the temperature of the heat treatment is 600 ℃ to 1200 ℃, and the time of the heat treatment is 1 hour to 6 hours. Further, the temperature of the heat treatment is 850-1150 ℃, and the time of the heat treatment is 2-4 hours.
The invention also provides a silicon-oxygen anode material which is prepared by the preparation method of the silicon-oxygen anode material; the silicon-oxygen cathode material comprises an inner core, a first shell layer and a second shell layer.
The first shell layer is wrapped on the surface of the core, and the second shell layer is wrapped on the surface of the first shell layer.
The inner core is silicon oxide, and the mass ratio of silicon to oxygen in the silicon oxide is 1: (0.85-1.2); the first shell layer is silicon carbide; the second shell layer is a fluorocarbon-containing layer doped with a conductive agent.
The silica negative electrode material comprises an inner core, a first shell layer wrapping the inner core and a second shell layer wrapping the first shell layer; the core, the first shell and the second shell are respectively silicon oxide (SiO)x) Silicon carbide and a fluorocarbon-containing layer doped with a conductive agent. The silicon carbide of the first shell layer wraps the inner core to form an artificial SEI film,the first shell layer is wrapped by the fluorocarbon layer doped with the conductive agent of the second shell layer, so that the second shell layer has good conductivity, and an artificial SEI (solid electrolyte interphase) film (LiF) can be further generated to protect a silicon-oxygen negative electrode material in the charging process. The shell layer of the silicon-oxygen negative electrode material is opposite to the silicon oxide (SiO) of the inner core through the combination of a specific conductive agent and an organic fluorine-containing carbon sourcex) The coating property is strong, and the conductive agent and the fluorine-containing carbon source can be effectively coated on silicon oxide (SiO)x) The surface modification is carried out, the silicon-oxygen negative electrode material has better stability and excellent electrochemical performance, the first charge efficiency, the cycle performance and the rate performance of the silicon-oxygen negative electrode material are good, the cycle stability is high, and the powder conductivity of the silicon-oxygen negative electrode material reaches 2.1 multiplied by 10-4S/m, the first charge efficiency exceeds 78%, and the capacity retention rate exceeds 80% after 100 cycles.
In some of these embodiments, silicon oxide (SiO)x) The ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9-1.05). At this time, silicon oxide (SiO)x) Has better cycling stability and higher specific capacity.
The silicon carbide of the first shell layer has good mechanical property, and the silicon carbide coated on the surface of the silicon oxide of the inner core can be used as an artificial SEI (solid electrolyte interphase) film to prevent the permeation of electrolyte, so that the loss of the electrolyte and lithium salt is reduced, and the first charge efficiency of the silicon-oxygen negative electrode material is high; and can also stabilize the volume change of the silicon-oxygen anode material in the charge and discharge processes. In some embodiments, the first shell layer accounts for 0.05-1% of the silicon-oxygen negative electrode material by mass. Further, the first shell layer accounts for 0.2-0.5% of the silicon-oxygen cathode material by mass.
In some embodiments, the particulate conductive agent accounts for 0.001-2% of the silicon-oxygen negative electrode material by mass. Furthermore, the granular conductive agent accounts for 1-1.5% of the silicon-oxygen negative electrode material by mass.
In some embodiments, the sheet-shaped conductive agent accounts for 0.001-1.5% of the silicon-oxygen negative electrode material by mass. Furthermore, the sheet conductive agent accounts for 0.02-1% of the silicon-oxygen cathode material by mass.
In some embodiments, the fluorine-containing carbon layer accounts for 1% to 10% of the silicon-oxygen negative electrode material by mass. Further, the fluorine-containing carbon layer accounts for 2-6% of the silicon-oxygen negative electrode material by mass.
In some of these embodiments, the silicon oxygen anode material has a median particle size of 1 micron to 10 microns. Furthermore, the median particle size of the silicon-oxygen anode material is 4-8 microns.
In some of these embodiments, the radial dimension of the core is between 1 micron and 10 microns.
In some of these embodiments, the first shell layer has a thickness of 0.5 nm to 10 nm. Further, the thickness of the first shell layer is 3-5 nm.
In some of these embodiments, the second shell layer has a thickness of 10 nanometers to 50 nanometers. Further, the thickness of the second shell layer is 30-40 nm.
Another embodiment of the present invention also provides a lithium ion battery, wherein a negative active material of the lithium ion battery includes: the silicon-oxygen cathode material.
The negative plate of the lithium ion battery comprises the silica negative material, has good first charge efficiency, long cycle life, high cycle stability, higher energy density and good electrochemical performance.
The invention also provides a rechargeable product which contains the lithium ion battery.
In some of these embodiments, the rechargeable products include, but are not limited to, automobiles, cell phones, watches, and the like.
The following are specific examples. Unless otherwise specified, the parts in the following examples are parts by mass.
Example 1:
the silicon-oxygen anode material of the embodiment is prepared according to the following steps:
(1) mixing 15 parts of polyvinylidene fluoride and 85 parts of N-methyl pyrrolidone to obtain a fluorine-containing carbon source solution;
(2) mixing 1 part of graphene with a fluorine-containing carbon source solution to obtain a uniformly dispersed dispersion liquid;
(3) taking 100 parts of SiOxMixing with the dispersion, and sprayingCarrying out spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(4) transferring the mixed powder into a tube furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 900 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 5 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
Example 2:
the silicon-oxygen anode material of the embodiment is prepared according to the following steps:
(1) mixing 15 parts of polyvinylidene fluoride and 85 parts of N-methyl pyrrolidone to obtain a fluorine-containing carbon source solution;
(2) mixing 1 part of reduced graphene oxide with a fluorine-containing carbon source solution to obtain a uniformly dispersed dispersion liquid;
(3) taking 100 parts of SiOxMixing with the dispersion liquid, and spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(4) transferring the mixed powder into a tube furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 900 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 5 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
Example 3:
the silicon-oxygen anode material of the embodiment is prepared according to the following steps:
(1) mixing 12 parts of polyvinylidene fluoride and 88 parts of N-methyl pyrrolidone to obtain a fluorine-containing carbon source solution;
(2) mixing 1 part of graphene with a fluorine-containing carbon source solution to obtain a uniformly dispersed dispersion liquid;
(3) taking 100 parts of SiOxMixing with the dispersion liquid, and spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(4) transferring the mixed powder into a tubular furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 950 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 4 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
Example 4:
the silicon-oxygen anode material of the embodiment is prepared according to the following steps:
(1) mixing 20 parts of polychlorotrifluoroethylene with 80 parts of N-methyl pyrrolidone to obtain a fluorine-containing carbon source solution;
(2) mixing 1 part of graphene with a fluorine-containing carbon source solution to obtain a uniformly dispersed dispersion liquid;
(3) taking 100 parts of SiOxMixing with the dispersion liquid, and spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(4) transferring the mixed powder into a tube furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 1000 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 3 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
Example 5:
the silicon-oxygen anode material of the embodiment is prepared according to the following steps:
(1) mixing 15 parts of polyvinylidene fluoride-hexafluoropropylene copolymer and 85 parts of N-methyl pyrrolidone to obtain a fluorine-containing carbon source solution;
(2) mixing 1 part of graphene with a fluorine-containing carbon source solution to obtain a uniformly dispersed dispersion liquid;
(3) taking 100 parts of SiOxMixing with the dispersion liquid, and spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(4) transferring the mixed powder into a tube furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 1050 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 2 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
Example 6:
the silicon-oxygen anode material of the embodiment is prepared according to the following steps:
(1) mixing 15 parts of nitroso-type fluororubber and 85 parts of N-methyl pyrrolidone to obtain a fluorine-containing carbon source solution;
(2) mixing 1 part of Ketjen black with a fluorine-containing carbon source solution to obtain a uniformly dispersed dispersion liquid;
(3) taking 100 parts of SiOxMixing with the dispersion liquid, and spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(4) transferring the mixed powder into a tube furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 900 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 5 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
Example 7:
the silicon-oxygen anode material of the embodiment is prepared according to the following steps:
(1) mixing 15 parts of nitroso-type fluororubber and 85 parts of N-methyl pyrrolidone to obtain a fluorine-containing carbon source solution;
(2) mixing 1 part of conductive carbon black with a fluorine-containing carbon source solution to obtain a uniformly dispersed dispersion liquid;
(3) taking 100 parts of SiOxMixing with the dispersion liquid, and spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(4) transferring the mixed powder into a tube furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 900 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 5 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
Example 8:
the silicon-oxygen anode material of the embodiment is prepared according to the following steps:
(1) mixing 12 parts of fluorine-containing polyester fluororubber and 88 parts of N-methyl pyrrolidone to obtain a fluorine-containing carbon source solution;
(2) mixing 1 part of Ketjen black with a fluorine-containing carbon source solution to obtain a uniformly dispersed dispersion liquid;
(3) taking 100 parts of SiOxMixing with the dispersion liquid, and spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(4) transferring the mixed powder into a tubular furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 950 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 4 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
Example 9:
the silicon-oxygen anode material of the embodiment is prepared according to the following steps:
(1) mixing 20 parts of fluorosilicone rubber and 80 parts of N-methyl pyrrolidone to obtain a fluorine-containing carbon source solution;
(2) mixing 1 part of Ketjen black with a fluorine-containing carbon source solution to obtain a uniformly dispersed dispersion liquid;
(3) taking 100 parts of SiOxMixing with the dispersion liquid, and spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(4) transferring the mixed powder into a tube furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 1000 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 3 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
Example 10:
the silicon-oxygen anode material of the embodiment is prepared according to the following steps:
(1) mixing 15 parts of fluorine-containing polyacrylate fluororubber and 85 parts of N-methyl pyrrolidone to obtain a fluorine-containing carbon source solution;
(2) mixing 1 part of Ketjen black with a fluorine-containing carbon source solution to obtain a uniformly dispersed dispersion liquid;
(3) taking 100 parts of SiOxMixing with the dispersion liquid, and spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(4) transferring the mixed powder into a tube furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 1050 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 2 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
Comparative example 1:
the silicon-oxygen negative electrode material of the comparative example was prepared according to the following procedure:
(1) mixing 15 parts of polyvinylidene fluoride and 85 parts of N-methyl pyrrolidone to obtain a fluorine-containing carbon source solution;
(2) taking 100 parts of SiOxMixing with a fluorine-containing carbon source solution, and spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(3) transferring the mixed powder into a tube furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 900 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 5 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
Comparative example 2:
the silicon-oxygen negative electrode material of the comparative example was prepared according to the following procedure:
(1) mixing 15 parts of nitroso-type fluororubber and 85 parts of N-methyl pyrrolidone to obtain a fluorine-containing carbon source solution;
(2) taking 100 parts of SiOxMixing with a fluorine-containing carbon source solution, and spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(3) transferring the mixed powder into a tube furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 900 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 5 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
Comparative example 3:
the silicon-oxygen negative electrode material of the comparative example was prepared according to the following procedure:
(1) mixing 15 parts of polyethylene with 85 parts of N-methyl pyrrolidone to obtain a polyethylene solution;
(2) mixing 1 part of graphene with a polyethylene solution to obtain a uniformly dispersed dispersion liquid;
(3) taking 100 parts of SiOxMixing with the dispersion liquid, and spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(4) transferring the mixed powder into a tube furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 900 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 5 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
Comparative example 4:
the silicon-oxygen negative electrode material of the comparative example was prepared according to the following procedure:
(1) mixing 15 parts of polyethylene with 85 parts of N-methyl pyrrolidone to obtain a polyethylene solution;
(2) mixing 1 part of Ketjen black with a polyethylene solution to obtain a uniformly dispersed dispersion liquid;
(3) taking 100 parts of SiOxMixing with the dispersion liquid, and spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(4) transferring the mixed powder into a tube furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 900 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 5 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
Comparative example 5:
the silicon-oxygen negative electrode material of the comparative example was prepared according to the following procedure:
(1) mixing 15 parts of nitroso-type fluororubber and 85 parts of N-methyl pyrrolidone to obtain a fluorine-containing carbon source solution;
(2) mixing 1 part of reduced graphene oxide with a nitroso-fluorine rubber solution to obtain a uniformly dispersed dispersion liquid;
(3) taking 100 parts of SiOxMixing with the dispersion liquid, and spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(4) transferring the mixed powder into a tube furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 900 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 5 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
Comparative example 6:
the silicon-oxygen negative electrode material of the comparative example was prepared according to the following procedure:
(1) mixing 15 parts of polyvinylidene fluoride and 85 parts of N-methyl pyrrolidone to obtain a fluorine-containing carbon source solution;
(2) mixing 1 part of conductive carbon black with a fluorine-containing carbon source solution to obtain a uniformly dispersed dispersion liquid;
(3) taking 100 parts of SiOxMixing with dispersionMixing, and spray drying to obtain mixed powder; SiO 2xThe ratio of the amount of silicon and oxygen species in the mixture is 1: (0.9 to 1.05);
(4) transferring the mixed powder into a tube furnace, introducing nitrogen at the flow rate of 0.5L/min, heating to 900 ℃ at the heating rate of 5.0 ℃/min under the protection of the nitrogen, and preserving the heat for 5 hours; and crushing, screening and demagnetizing to obtain the silicon-oxygen negative electrode material.
The preparation conditions of examples 1 to 10 and comparative examples 1 to 6 can be found in Table 1.
TABLE 1
Figure BDA0003151990010000151
Figure BDA0003151990010000161
And (3) conductivity test:
a certain amount of the powder materials prepared in examples 1-10 and comparative examples 1-6 are respectively taken, pressed into a block by a flat press under the pressure of 20kN, and the conductivity of the block is tested by four probes.
And (3) testing electrical properties:
respectively taking the silica negative electrode materials prepared in the examples 1-10 and the comparative examples 1-6 as negative electrode active materials and LA136D as a binder, adding conductive carbon black, stirring, pulping, coating on a copper foil, and finally drying and rolling to prepare a negative electrode sheet, wherein the mass ratio of the negative electrode active materials to the conductive carbon black to the binder is 85:10: 5. Using a metallic lithium plate as a counter electrode, Celgard2400 diaphragm, LiPF6Ethylene Carbonate (EC) + diethyl carbonate (DEC) + dimethyl carbonate (DMC) as electrolyte, with a volume ratio of EC, DEC and DMC of 1:1:1, containing 5% wt. fluoroethylene carbonate (FEC), the button cell was assembled in an argon-filled glove box. The electrochemical performance of the battery is tested by adopting blue light, the charging and discharging voltage interval is 0.005V-2V, and the charging and discharging rate is 0.1C.
The conductivity and electrical properties test results are shown in table 2.
TABLE 2
Figure BDA0003151990010000171
As can be seen from the data in Table 2, the silicon-oxygen negative electrode materials prepared in the examples 1-10 have good comprehensive electrochemical properties, and the powder conductivity is 8.3 multiplied by 10-5S/m～4.2×10-4S/m, reversible capacity of 1486.1 mAh/g-1532.2 mAh/g, initial charge efficiency of 78.1% -79.5%, and capacity retention rate of 82.6% -86.9% after 100 cycles.
Compared with the silicon-oxygen anode materials only coated with the organic fluorine-containing carbon source in the comparative examples 1 and 2, the powder conductivity, reversible capacity, initial charge efficiency and capacity retention rate of the silicon-oxygen anode materials in the examples 1-10 are greatly improved, and the fact that the electrochemical performance of the anode material can be improved by doping the conductive agent in the silicon-oxygen anode material is demonstrated.
Compared with the silicon-oxygen cathode materials of comparative examples 3 and 4 coated with polyethylene and a conductive agent, the first charge efficiency and the capacity retention rate of the silicon-oxygen cathode materials of examples 1 to 10 are significantly improved, which is probably because the organic fluorine-containing carbon source adopted in examples 1 to 10 has stronger reactivity compared with polyethylene, can react with silicon oxide to form silicon nitride, plays a role in protecting and stabilizing the volume change of the core, and the fluorine element is easy to form LiF with lithium ions to serve as an artificial SEI film during charging, so that the cycle stability of the cathode materials is further improved.
Compared with comparative examples 5 and 6, the powder conductivity, reversible capacity, first charge efficiency and capacity retention rate of the silicon-oxygen anode materials of examples 1-10 are obviously improved. This is because the dispersions of examples 1 to 10, which are a combination of a linear fluoropolymer and a sheet-like conductive agent (examples 1 to 5) or a combination of a crosslinked fluoropolymer and a particulate conductive agent (examples 6 to 10), have a good coating property, and therefore, a uniform coating layer can be formed on the surface of silicon oxide, and the rate capability and cycle performance of the negative electrode material can be improved. The dispersions in the comparative examples 5 and 6 are respectively the combination of the nitroso fluororubber and the reduced graphene oxide or the combination of the polyvinylidene fluoride and the conductive carbon black, so that the coating property is poor, the particles are easy to agglomerate or fall off on the surface of the silicon oxide, the modification effect is poor, and the electrochemical performance is poor.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.

Claims (10)

1. The preparation method of the silicon-oxygen anode material is characterized by comprising the following steps of:
dispersing an organic fluorine-containing carbon source and a conductive agent in a solvent to obtain a dispersion liquid, wherein the organic fluorine-containing carbon source is a linear fluorine-containing polymer and the conductive agent is a sheet conductive agent, or the organic fluorine-containing carbon source is a cross-linked fluorine-containing polymer and the conductive agent is a granular conductive agent;
mixing silicon oxide with the dispersion liquid, and drying to obtain mixed powder, wherein the mass ratio of silicon to oxygen of the silicon oxide is 1: (0.85-1.2);
and carrying out heat treatment on the mixed powder under the protection of protective gas.
2. The method for producing a silicone negative electrode material according to claim 1, wherein the linear fluoropolymer is at least one selected from the group consisting of polyvinylidene fluoride, polymerized tetrafluoroethylene, a polyvinylidene fluoride-hexafluoropropylene copolymer, polychlorotrifluoroethylene, and a tetrafluoroethylene-ethylene copolymer.
3. The method for preparing a silicon-oxygen anode material according to claim 1, wherein the sheet-like conductive agent is at least one selected from graphene, reduced graphene oxide and graphene nanoribbons.
4. The method for preparing a silicon-oxygen negative electrode material according to claim 1, wherein the cross-linked fluoropolymer is at least one selected from the group consisting of nitroso-type fluororubbers, fluorine-containing polyester-type fluororubbers, fluorosilicone rubbers and fluorine-containing polyacrylate fluororubbers.
5. The method for producing a silicon-oxygen negative electrode material according to claim 1, wherein the particulate conductive agent is at least one selected from the group consisting of conductive carbon black, ketjen black, and furnace black.
6. The method for preparing the silicon-oxygen anode material according to any one of claims 1 to 5, wherein the mass ratio of the organic fluorine-containing carbon source to the conductive agent to the silicon oxide is (12-20): 1: (95-105).
7. The method for preparing a silicon-oxygen anode material according to any one of claims 1 to 5, wherein the temperature of the heat treatment is 600 ℃ to 1200 ℃, and the time of the heat treatment is 1 hour to 6 hours.
8. A silicon-oxygen anode material, which is obtained by the preparation method of the silicon-oxygen anode material according to any one of claims 1 to 7; the silica anode material comprises an inner core, a first shell layer and a second shell layer;
the first shell layer is wrapped on the surface of the inner core; the second shell layer is wrapped on the surface of the first shell layer;
the inner core is silicon oxide, and the mass ratio of silicon to oxygen in the silicon oxide is 1: (0.85-1.2); the first shell layer is made of silicon carbide; the second shell layer is a fluorocarbon-containing layer doped with a conductive agent.
9. A lithium ion battery, wherein the negative electrode sheet of the lithium ion battery contains the silica negative electrode material according to claim 8.
10. A rechargeable product comprising the lithium ion battery according to claim 9.
CN202110769147.7A 2021-07-07 2021-07-07 Lithium ion battery, silica negative electrode material, and preparation method and application thereof Pending CN113307272A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110769147.7A CN113307272A (en) 2021-07-07 2021-07-07 Lithium ion battery, silica negative electrode material, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110769147.7A CN113307272A (en) 2021-07-07 2021-07-07 Lithium ion battery, silica negative electrode material, and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN113307272A true CN113307272A (en) 2021-08-27

Family

ID=77382009

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110769147.7A Pending CN113307272A (en) 2021-07-07 2021-07-07 Lithium ion battery, silica negative electrode material, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113307272A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114551872A (en) * 2022-01-19 2022-05-27 惠州市豪鹏科技有限公司 Negative electrode material, preparation method thereof, battery negative electrode and battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109167031A (en) * 2018-08-21 2019-01-08 浙江大学 A kind of nano-silicone wire/carbon composite material and its preparation method and application
CN112635727A (en) * 2020-12-10 2021-04-09 安普瑞斯（南京）有限公司 Silica particles with core-shell structure, preparation method thereof, negative electrode material and battery
CN112687853A (en) * 2020-12-10 2021-04-20 安普瑞斯（南京）有限公司 Silica particle aggregate, preparation method thereof, negative electrode material and battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109167031A (en) * 2018-08-21 2019-01-08 浙江大学 A kind of nano-silicone wire/carbon composite material and its preparation method and application
CN112635727A (en) * 2020-12-10 2021-04-09 安普瑞斯（南京）有限公司 Silica particles with core-shell structure, preparation method thereof, negative electrode material and battery
CN112687853A (en) * 2020-12-10 2021-04-20 安普瑞斯（南京）有限公司 Silica particle aggregate, preparation method thereof, negative electrode material and battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114551872A (en) * 2022-01-19 2022-05-27 惠州市豪鹏科技有限公司 Negative electrode material, preparation method thereof, battery negative electrode and battery
CN114551872B (en) * 2022-01-19 2024-02-27 惠州市豪鹏科技有限公司 Negative electrode material, preparation method thereof, battery negative electrode and battery

Similar Documents

Publication Publication Date Title
CN111987296B (en) Negative electrode material, and electrochemical device and electronic device using same
CN110444750B (en) Negative electrode material, and electrochemical device and electronic device comprising same
US10826130B2 (en) Negative active material and preparation method thereof and secondary battery
CN112467118B (en) Graphite composite material, preparation method thereof and lithium battery cathode
CN113471442B (en) Negative active material, and negative electrode sheet, electrochemical device, and electronic device using same
CN101179123B (en) Method for producing anode of lithium ion battery
CN113555539A (en) High-energy-density quick-charging graphite composite negative electrode material, preparation method thereof and lithium ion battery
JP2024501526A (en) Negative electrode pieces, electrochemical devices and electronic devices
CN111146433B (en) Negative electrode, electrochemical device and electronic device including the same
CN111883765A (en) Lithium battery positive active material, preparation method thereof and lithium battery
CN113307272A (en) Lithium ion battery, silica negative electrode material, and preparation method and application thereof
CN115548424B (en) Electrochemical device and electronic device
CN113196524A (en) Negative electrode material, negative electrode sheet, electrochemical device, and electronic device
CN111755665A (en) Lithium ion battery negative electrode material, battery negative electrode and application thereof
CN115440933A (en) Negative pole piece, battery package and consumer
CN116670846A (en) Secondary battery and electricity device comprising same
CN114097108A (en) Cathode material, preparation method thereof, electrochemical device and electronic device
CN116134642A (en) Positive electrode material, electrochemical device and electronic device including the same
JP2022534460A (en) Negative electrode mixture and its use
WO2024011482A1 (en) Negative electrode plate, rechargeable battery, battery module, battery pack and electric apparatus
CN116314603B (en) Negative electrode plate, electrochemical device and electronic device
KR102539166B1 (en) Fast-charging long-life secondary batteries, battery modules, battery packs, and electrical devices
WO2024011539A1 (en) Negative electrode sheet, secondary battery, battery module, battery pack, and electric apparatus
CN113348570B (en) Electrochemical device and electronic device
CN113437299B (en) Negative electrode active material, electrochemical device, and electronic device

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
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20210827