CN113964303A - Silicon composite negative electrode material, preparation method thereof and secondary battery - Google Patents

Silicon composite negative electrode material, preparation method thereof and secondary battery Download PDF

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CN113964303A
CN113964303A CN202111176105.9A CN202111176105A CN113964303A CN 113964303 A CN113964303 A CN 113964303A CN 202111176105 A CN202111176105 A CN 202111176105A CN 113964303 A CN113964303 A CN 113964303A
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silicon
silicon composite
negative electrode
copper
graphene
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薛冬峰
彭超
王晓明
王鑫
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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Priority to PCT/CN2021/137617 priority patent/WO2023056706A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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 application belongs to the technical field of batteries, and particularly relates to a silicon composite negative electrode material, a preparation method thereof and a secondary battery. The silicon composite negative electrode material is of a core-shell structure and comprises a silicon-based material core, and a middle layer and an outer shell which are sequentially coated on the outer surface of the core; wherein the intermediate layer comprises a carbon nanomaterial loaded with a metal element, and the outer shell layer comprises an amorphous carbon material. The silicon composite negative electrode material provided by the application has the advantages that the silicon composite negative electrode material has excellent specific capacity, good structural stability and high ion electron migration transmission efficiency through the synergistic effect of the core silicon-based material, the carbon nano material with the metal element loaded in the middle layer and the outer shell amorphous carbon material, and the electrochemical properties of the battery such as energy density, cycle life, safety and the like can be effectively improved.

Description

Silicon composite negative electrode material, preparation method thereof and secondary battery
Technical Field
The application belongs to the technical field of batteries, and particularly relates to a silicon composite negative electrode material, a preparation method thereof and a secondary battery.
Background
At present, the theoretical specific capacity of graphite negative electrode materials widely adopted by lithium ion batteries is only 372mAh g-1And the theoretical specific capacity of the silicon reaches 4200mAh g-1And the lithium intercalation potential is lower than 0.5V. The silicon is abundant in the earth, low in price and environment-friendly. Under the urgent need of improving the performance of the lithium ion battery, silicon is expected to become a new generation of high-capacity cathode material. However, the lithium ion battery silicon negative electrode material has these bottleneck problems during the charging and discharging process: (1) the volume expansion of silicon can exceed 300 percent in the lithiation/delithiation process, so that the problems of particle cracking, pulverization, falling and the like are caused, and finally the performance of the battery is attenuated; (2) in the charging and discharging process, due to the constant change of the electrode volume, a Solid Electrolyte Interface (SEI) on the surface of the silicon cathode can be repeatedly damaged and regenerated, so that the problems of reduction of the conductive capacity of the material, reduction of the charging and discharging efficiency and the like are caused; (3) the silicon has poor conductivity, and the diffusion coefficient of lithium ions in the silicon material is small, so that the power density of the silicon negative electrode material is poor, and the requirement of high specific capacity is difficult to achieve.
In contrast, in the aspect of composite material structure design, a plurality of yolk-shell structures are adopted, and the yolk-shell structure silicon carbon material which takes carbon as a shell and silicon as a core is generally adopted, and a certain gap is formed between the core and the shell. The structure can provide a buffer layer for the volume expansion of the electrode, and avoid the direct contact of the silicon cathode and the electrolyte, thereby improving the problem of instability of the SEI film. Although the prior art alleviates the problems associated with the volume change of silicon to some extent, there is still room for improvement in improving the ionic conductivity and electronic conductivity of the silicon negative electrode.
Disclosure of Invention
The application aims to provide a silicon composite negative electrode material, a preparation method thereof and a secondary battery, and aims to solve the problems of large volume expansion and poor ionic and electronic conductivity of the existing silicon-based material to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the application provides a silicon composite negative electrode material, which is a core-shell structure and comprises a silicon-based material core, and a middle layer and an outer shell which are sequentially coated on the outer surface of the core; wherein the intermediate layer comprises a carbon nanomaterial loaded with a metal element, and the outer shell layer comprises an amorphous carbon material.
Further, in the carbon nanomaterial loaded with the metal element, the metal element includes: at least one of copper and silver.
Further, in the metal element-loaded carbon nanomaterial, the carbon nanomaterial includes: at least one of graphene and carbon nanotubes.
Furthermore, in the carbon nanomaterial loaded with the metal elements, the loading amount of the metal elements is 18-23 wt%.
Further, the metal element-loaded carbon nanomaterial is selected from: copper-graphene composites.
Further, in the silicon composite negative electrode material, the mass ratio of the silicon-based material core to the intermediate layer to the outer shell layer is 1: (0.5-0.8): (0.5-0.8).
Furthermore, in the silicon composite negative electrode material, the particle size D50 of the silicon-based material core is 200 nm-1 μm, the thickness of the middle layer is 100 nm-1 μm, and the thickness of the outer shell layer is 100 nm-1 μm.
Further, the silicon-based material is selected from: at least one of silicon simple substance, silicon oxide and silicon carbide.
In a second aspect, the present application provides a method for preparing a silicon composite anode material, comprising the steps of:
preparing a carbon nano material loaded with metal elements;
obtaining a silicon-based material, and forming a coating middle layer on the surface of the silicon-based material by using the carbon nano material loaded with the metal element to obtain an intermediate product;
and preparing an outer shell layer of the amorphous carbon material on the outer surface of the intermediate product to obtain the silicon composite anode material.
Further, the step of preparing the metal element-loaded carbon nanomaterial includes: and modifying the complexing agent on the surface of the carbon nano material, complexing with metal salt, and reducing the metal salt to obtain the carbon nano material loaded with the metal element.
Further, the step of forming the clad intermediate layer includes: and mixing the carbon nano material loaded with the metal element and the silicon-based material, and then drying in vacuum to obtain an intermediate product of which the middle layer is coated with the silicon-based material.
Further, the step of preparing the outer shell layer of amorphous carbon material comprises: and mixing the intermediate product with an amorphous carbon source, and performing vapor deposition to form an outer shell layer of the amorphous carbon material, thereby obtaining the silicon composite anode material.
Further, the complexing agent is selected from: at least one of octadecylamine, ethylenediamine, sec-butylamine, dodecylamine and hexadecylamine.
Further, the metal salt is selected from: at least one of copper salt and silver salt.
Further, the carbon nanomaterial is selected from: at least one of graphene and carbon nanotubes.
Further, the amorphous carbon source is selected from the group consisting of: glucose, citric acid, asphalt, phenolic resin, and epoxy resin.
Further, in the silicon composite negative electrode material, the mass ratio of the silicon-based material core to the intermediate layer to the outer shell layer is 1: (0.5-0.8): (0.5-0.8).
Further, the carbon nanomaterial loaded with the metal element is selected from a copper-graphene composite material, and the step of preparing the copper-graphene composite material comprises the following steps:
mixing and grinding the complexing agent and the graphene to obtain complexing agent modified graphene;
and dissolving the copper salt and the graphene modified by the complexing agent in an organic solvent, and adding a reducing agent to reduce the copper salt to obtain the copper-graphene composite material.
Further, the copper salt is selected from: cu (CH)3COO)2·H2O, copper sulfate, copper acetate and copper chloride.
Further, the mass ratio of the copper salt to the complexing agent-modified graphene is (0.01-2): 1.
further, the reducing agent is selected from: at least one of acetaldehyde, hydrazine hydrate, sodium borohydride, formaldehyde and propionaldehyde.
Further, the organic solvent is selected from: at least one of sec-butyl alcohol, tert-butyl alcohol and ethanol.
In a third aspect, the present application provides a secondary battery, wherein a negative plate of the secondary battery comprises the silicon composite negative electrode material, or comprises the silicon composite negative electrode material prepared by the method.
The silicon composite negative electrode material provided by the first aspect of the application is of a core-shell structure and comprises a silicon-based material core with high theoretical specific capacity, and a middle layer and a shell layer which are sequentially coated on the outer surface of the core; on one hand, the toughness of the metal and the flexibility of the carbon nanomaterial enable the middle layer to well absorb stress generated by the violent change of the volume of the core silicon-based material, so that adverse effects such as damage of a pole piece and the like caused by the volume change of the silicon-based material are avoided; on the other hand, the metal and carbon nano material has high ionic or electronic conductivity, and can effectively improve the transfer rate of lithium ions and electrons between the amorphous carbon material outer shell layer and the silicon-based material inner core, so that the integral power density of the silicon composite negative electrode material is improved. In addition, the outer shell layer comprises an amorphous carbon material which has higher reversible specific capacity, higher conductivity and good compatibility with electrolyte, and has a certain buffer effect on the volume change of the core silicon nano material.
The preparation method of the silicon composite anode material provided by the second aspect of the application has the advantages of simple process flow and high efficiency, and is suitable for industrial large-scale production and application. The prepared silicon composite anode material with the structure of the inner core silicon-based material, the carbon nano material with the middle layer loaded with the metal element and the outer shell amorphous carbon material has excellent specific capacity, good structural stability and high ion electron migration transmission efficiency, and can effectively improve the electrochemical properties of the battery, such as energy density, cycle life, safety and the like.
According to the secondary battery provided by the third aspect of the application, the negative plate of the secondary battery comprises the silicon composite negative electrode material, and the silicon composite negative electrode material has excellent specific capacity, good structural stability and high ion electron migration transmission efficiency, so that the electrochemical properties of the secondary battery, such as energy density, cycle life, safety and the like, can be effectively improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a silicon composite anode material provided in an embodiment of the present application;
fig. 2 is a schematic flow chart of a preparation method of a silicon composite anode material provided in an embodiment of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
As shown in fig. 1, a first aspect of the embodiments of the present application provides a silicon composite anode material, where the silicon composite anode material is a core-shell structure, and includes a silicon-based material core, and a middle layer and a shell layer that are sequentially coated on an outer surface of the core; wherein the intermediate layer comprises a carbon nanomaterial loaded with a metal element, and the outer shell layer comprises an amorphous carbon material.
The silicon composite negative electrode material provided by the first aspect of the embodiment of the application is of a core-shell structure and comprises a silicon-based material core with high theoretical specific capacity, and a middle layer and a shell layer which are sequentially coated on the outer surface of the core; on one hand, the toughness of the metal and the flexibility of the carbon nanomaterial enable the middle layer to well absorb stress generated by the violent change of the volume of the core silicon-based material, so that adverse effects such as damage of a pole piece and the like caused by the volume change of the silicon-based material are avoided; on the other hand, the metal and carbon nano material has high ionic or electronic conductivity, and can effectively improve the transfer rate of lithium ions and electrons between the amorphous carbon material outer shell layer and the silicon-based material inner core, so that the integral power density of the silicon composite negative electrode material is improved. In addition, the outer shell layer comprises an amorphous carbon material which has higher reversible specific capacity, higher conductivity and good compatibility with electrolyte, and has a certain buffer effect on the volume change of the core silicon nano material. Therefore, the silicon composite negative electrode material provided by the embodiment of the application has excellent specific capacity, good structural stability and high ion electron transfer transmission efficiency through the synergistic effect of the core silicon-based material, the carbon nano material with the middle layer loaded with the metal element and the shell amorphous carbon material, and can effectively improve the electrochemical properties of the battery, such as energy density, cycle life, safety and the like.
In some embodiments, in the carbon nanomaterial loaded with the metal element, the metal element includes: at least one of copper and silver; the metal elements not only have excellent electron migration and transmission performance, but also improve the diffusion rate of electrons between the inner core and the outer shell; and the core silicon-based material has excellent ductility and toughness, can well absorb the stress generated by the volume drastic change of the core silicon-based material in the charging and discharging process, reduces the volume change of the pole piece, improves the stability of the pole piece, prevents the pole piece from cracking, falling powder and the like, and improves the cycling stability of the battery.
In some embodiments, in the metal element-loaded carbon nanomaterial, the carbon nanomaterial includes: at least one of graphene and carbon nanotubes; the carbon nano materials have excellent ionic conductivity, and can improve the ion embedding and removing effect of the battery in the charging and discharging processes, thereby improving the rate capability of the battery. In addition, the carbon nano materials are easy to form an intermediate coating layer with a loose structure through acting forces such as Van der Waals force and the like, so that a buffer space is provided for volume change of the core silicon-based material in the charging and discharging processes, and the stability of the silicon nano core material is further improved.
In the middle layer of the silicon negative electrode material, metal is loaded in the carbon nano material, so that the load uniformity of metal elements can be improved, the volume deformation of the silicon-based material of the inner core is relieved through the synergistic effect of the metal elements and the carbon nano material, and the migration transmission efficiency of ionic electrons in the inner core and the outer shell is improved. In some embodiments, the loading amount of the metal element in the carbon nanomaterial loaded with the metal element is 18-23 wt%, and the loading amount fully ensures the effect of the intermediate layer on relieving the volume deformation of the core silicon-based material, and simultaneously ensures the gram volume of the silicon-based composite material. If the loading amount of the metal element is too high, the gram capacity of the silicon composite negative electrode material can be obviously reduced because the metal element and the carbon nano material can not participate in the ion deintercalation cycle in the charging and discharging processes of the battery, so that the energy density of the battery is reduced. When the metal simple substance directly forms an independent coating layer, the gram capacity of the silicon composite cathode material can be obviously reduced, and the metal simple substance coating layer can influence the embedding and extracting efficiency of lithium ion plasma in the core silicon-based material, so that the multiplying power performance of the battery is reduced.
In some embodiments, the metal element-loaded carbon nanomaterial is selected from: copper-graphene composites. In the intermediate layer formed by the copper-graphene composite material in the embodiment of the application, on one hand, the toughness of copper and the flexibility of graphene enable the intermediate layer to well absorb stress generated by the violent volume change of the core silicon-based material, so that adverse effects caused by the volume change are avoided; on the other hand, the high ionic conductivity of copper and graphene can effectively improve the diffusion rate of lithium ions between the amorphous carbon outer shell layer and the silicon-based material inner core, so that the overall power density of the negative electrode material is improved.
In some embodiments, in the silicon composite anode material, the mass ratio of the silicon-based material core, the middle layer and the outer shell layer is 1: (0.5-0.8): (0.5 to 0.8); the proportion fully ensures the comprehensive performances of the silicon composite negative electrode material such as specific capacity, structural stability, cycle performance and the like. If the proportion of the middle layer or the outer shell layer is too low, the volume deformation relieving effect of the core silicon-based material in the charging and discharging process is poor, the stability of the cathode material is difficult to improve, and the migration and transmission effects of ions and electrons in the silicon composite cathode material are not favorably improved; if the proportion of the intermediate layer or the outer shell layer is too high, the content of the silicon-based material is reduced, so that the gram capacity of the negative electrode material is reduced, and the energy density of the battery is reduced. In some embodiments, the mass ratio of the silicon-based material core, the intermediate layer, and the outer shell layer in the silicon composite anode material includes, but is not limited to, 1: 0.5: 0.5, 1: 0.5: 0.6, 1: 0.5: 0.7, 1: 0.5: 0.8, 1: 0.6: 0.8, 1: 0.7: 0.8, 1: 0.8: 0.8, 1: 0.6: 0.7, 1: 0.7: 0.6, 1: 0.8: 0.7, etc.
In some embodiments, in the silicon composite negative electrode material, the particle size D50 of the inner core of the silicon-based material is 200nm to 1 μm, preferably 200 to 500nm, the thickness of the middle layer is 100nm to 1 μm, preferably 100 to 500nm, and the thickness of the outer shell layer is 100nm to 1 μm, preferably 100 to 500 nm. In the silicon composite negative electrode material, the particle size of the core of the silicon-based material and the thicknesses of the middle layer and the shell layer also effectively ensure the comprehensive performances of the silicon composite negative electrode material, such as specific capacity, structural stability, cycle performance and the like, and the ghost composite negative electrode material has a larger specific surface area, so that a larger active specific surface area is provided for the de-intercalation of lithium ions, and the cycle charge and discharge efficiency of the battery is improved. If the middle layer or the outer shell layer is too thin, the volume deformation relieving effect of the core silicon-based material in the charging and discharging process is poor, the stability of the cathode material is difficult to improve, and the migration and transmission effects of ions and electrons in the silicon composite cathode material are not favorably improved; if the intermediate layer or the outer shell layer is too thick, the content of the silicon-based material is reduced, so that the gram capacity of the negative electrode material is reduced, and the energy density of the battery is reduced.
In some embodiments, the silicon-based material is selected from: at least one of silicon simple substance, silicon oxide and silicon carbide, and the silicon-based materials have high theoretical specific capacity and can effectively improve the energy density of the battery.
The silicon composite anode material of the embodiment of the application can be prepared by the following embodiment method.
As shown in fig. 2, a second aspect of the embodiments of the present application provides a method for preparing a silicon composite anode material, including the following steps:
s10, preparing a carbon nano material loaded with metal elements;
s20, obtaining a silicon-based material, and forming an intermediate coating layer on the surface of the silicon-based material by using the carbon nano material loaded with the metal element to obtain an intermediate product;
s30, preparing an outer shell layer of the amorphous carbon material on the outer surface of the intermediate product to obtain the silicon composite negative electrode material.
In the preparation method of the silicon composite anode material provided in the second aspect of the embodiment of the present application, after the carbon nanomaterial loaded with the metal element is prepared, a coating intermediate layer is formed on the surface of the silicon-based material, and then an outer shell layer of the amorphous carbon material is prepared, so as to obtain the silicon composite anode material with the core-shell structure including the silicon-based material core-the carbon nanomaterial intermediate layer loaded with the metal element-the amorphous carbon material outer shell layer. The preparation method of the silicon composite anode material in the embodiment of the application has the advantages of simple process flow and high efficiency, and is suitable for industrial large-scale production and application. The prepared silicon composite anode material with the structure of the inner core silicon-based material, the carbon nano material with the middle layer loaded with the metal element and the outer shell amorphous carbon material has excellent specific capacity, good structural stability and high ion electron migration transmission efficiency, and can effectively improve the electrochemical properties of the battery, such as energy density, cycle life, safety and the like.
In some embodiments, in the step S10, the step of preparing the carbon nanomaterial loaded with the metal element includes: and modifying the complexing agent on the surface of the carbon nano material, complexing with metal salt, and reducing the metal salt to obtain the carbon nano material loaded with the metal element. According to the embodiment of the application, the complexing agent is modified to the surface of the carbon nano material, then the metal salt is uniformly complexed on the surface of the carbon nano material through the complexing agent, and then the metal salt is reduced into the metal simple substance, so that the metal simple substance is uniformly and stably loaded in the carbon nano material, and the carbon nano material loaded with the metal element is obtained. In addition, the loading amount of the metal elements in the carbon nano material can be controlled by changing the quantity and the type of the complexing agent for surface modification of the carbon nano material.
In some embodiments, the complexing agent is selected from: at least one of octadecylamine, ethylenediamine, sec-butylamine, dodecylamine and hexadecylamine; the complexing agents can be modified on the surface of the carbon nano material to form the carbon nano material modified with the complexing agents on the surface. In addition, the complexing agents have good complexing effect on metal salts through ammonium ions, and can form highly uniform and stably dispersed dispersion liquid of the carbon nano material-organic amine-metal ion complex.
In some embodiments, the metal salt is selected from: at least one of copper salt and silver salt; the metal elements in the metal salts not only have excellent electron migration and transmission performance, but also improve the diffusion rate of electrons between the inner core and the outer shell; and the core silicon-based material has excellent ductility and toughness, can well absorb the stress generated by the volume drastic change of the core silicon-based material in the charging and discharging processes, reduces the volume change of the pole piece, and improves the stability of the pole piece.
In some embodiments, the carbon nanomaterial is selected from: at least one of graphene and carbon nanotubes; firstly, the surfaces of the carbon nano materials often contain more defect sites or active groups such as hydroxyl groups and the like, which is beneficial to the attachment and modification of complexing agents. In addition, the carbon nano materials have excellent ion conductivity, and can improve the ion embedding and removing effect of the battery in the charging and discharging processes, so that the rate capability of the battery is improved. In addition, the carbon nano materials are easy to form an intermediate coating layer with a loose structure through acting forces such as Van der Waals force and the like, so that a buffer space is provided for volume change of the core silicon-based material in the charging and discharging processes, and the stability of the silicon nano core material is further improved.
In some embodiments, the metal element-loaded carbon nanomaterial is selected from a copper-graphene composite, and the step of preparing the copper-graphene composite comprises:
s11, mixing and grinding a complexing agent and graphene to obtain graphene modified by the complexing agent;
s12, dissolving copper salt and graphene modified by a complexing agent in an organic solvent, and adding a reducing agent to reduce the copper salt to obtain the copper-graphene composite material.
In some embodiments, in step S11, graphite flakes and complexing agents such as octadecylamine, ethylenediamine, sec-butylamine, dodecylamine, hexadecylamine, etc. may be dissolved and dispersed in an organic solvent, and then, a grinding and mixing process is performed, preferably, ball milling is performed at a rotation speed of 400r/min for 24 hours, then, the ground products are separated in different centrifugation intervals, so as to obtain centrifugation products in different centrifugation intervals, and then, the centrifugation products in different intervals are settled, centrifuged, and washed, so as to obtain graphene modified by the complexing agents, which is dispersed in the organic solvent to form a dispersion for later use.
In some embodiments, the organic solvent is selected from: the organic solvents have good dissolving effect on complexing agents such as octadecylamine, ethylenediamine, sec-butylamine, dodecylamine and hexadecylamine, and also have good dispersing effect on graphene raw materials or graphene.
In some embodiments, in step S12, after the copper salt and the graphene modified by the complexing agent are dissolved in an organic solvent such as sec-butyl alcohol to form a highly uniform and stable graphene-organic amine-copper complex dispersion, a reducing agent is added to reduce the copper salt, so as to form the copper-graphene composite material.
In some embodiments, the copper salt is selected from: cu (CH)3COO)2·H2At least one of O, copper sulfate, copper acetate and copper chlorideOne kind of copper salt has high dissolving and dispersing effect in sec-butyl alcohol and other solvent and high complexing effect with complexing agent.
In some embodiments, the reducing agent is selected from: at least one of acetaldehyde, hydrazine hydrate, sodium borohydride, formaldehyde and propionaldehyde; the reducing agents can reduce copper salt into copper simple substance, so that the copper simple substance is uniformly, stably and stably loaded in the graphene material.
In some embodiments, the mass ratio of the copper salt to the complexing agent-modified graphene is (0.01-2): 1; the proportion fully ensures the loading effect of the copper salt in the graphene, thereby ensuring the effect of the formed copper-graphene composite material interlayer on relieving the volume deformation of the core silicon-based material, and simultaneously ensuring the gram volume of the silicon-based composite material. If the copper salt addition ratio is too high, the graphene is difficult to be completely loaded in, the subsequent impurity removal difficulty is increased, and if the copper salt addition ratio is too low, the metal elements loaded on the surface of the graphene are too few, which is not beneficial to improving the stability and the ion electron conduction efficiency of the silicon composite anode material. In some embodiments, the mass ratio of the copper salt to the complexing agent-modified graphene includes, but is not limited to (0.01-0.1): 1. (0.1-0.5): 1. (0.5-1): 1. (1-1.5): 1. (1.5-2): 1, etc.
In some embodiments, in the step S20, the step of forming the cladding interlayer includes: and mixing the carbon nano material loaded with the metal element and the silicon-based material, and then drying in vacuum to prevent copper from being oxidized in a high-temperature environment, thereby obtaining an intermediate product of which the silicon-based material is coated by the intermediate layer. In some specific embodiments, a certain amount of micron silicon is immersed in a dispersion liquid of a high-concentration copper-graphene composite material, uniformly mixed and ultrasonically dispersed, and then dried in a vacuum freeze drying oven for 10 hours to form a copper-graphene composite material interlayer, so as to obtain an intermediate product of which the surface of the silicon material core is coated by the interlayer.
In some embodiments, in the step S30, the step of preparing the outer shell layer of amorphous carbon material comprises: and mixing the intermediate product with an amorphous carbon source, and performing vapor deposition to form an outer shell layer of the amorphous carbon material to obtain the silicon composite anode material. In some embodiments, the amorphous carbon source is selected from: glucose, citric acid, asphalt, phenolic resin, and epoxy resin. In the embodiments of the present application, after the intermediate product is mixed with the amorphous carbon source, the amorphous carbon source is converted to an amorphous carbon material clad shell layer by vapor deposition at a high temperature.
In some embodiments, the intermediate product and a certain amount of amorphous carbon source are mixed by ball milling for 8-12 hours under a vibration ball mill according to a mass ratio of 10:3, 10:4 or 10:5, and then are uniformly mixed and ultrasonically dispersed, and then are dried for 8-15 hours in a vacuum drying oven at 40-60 ℃. Then the ball-milled product is put into a tube furnace for chemical vapor deposition in Ar/H2Heating to 400-900 ℃ from room temperature at a speed of 1-10 ℃/min under inert atmosphere, and then heating to C2H2and/Ar or the like in an atmosphere containing a carbon source for 30 to 60 minutes. And after chemical vapor deposition, cooling the product in a furnace, cleaning the product in solutions of hydrochloric acid, hydrofluoric acid, water, ethanol and the like, and drying the product in vacuum to obtain the silicon composite negative electrode material.
In some embodiments, in the silicon composite anode material, the mass ratio of the silicon-based material core, the middle layer and the outer shell layer is 1: (0.5-0.8): (0.5-0.8), and the proportion fully ensures the comprehensive performances of the silicon composite negative electrode material such as specific capacity, structural stability, cycle performance and the like. If the proportion of the middle layer or the outer shell layer is too low, the volume deformation relieving effect of the core silicon-based material in the charging and discharging process is poor, the stability of the cathode material is difficult to improve, and the migration and transmission effects of ions and electrons in the silicon composite cathode material are not favorably improved; if the proportion of the intermediate layer or the outer shell layer is too high, the content of the silicon-based material is reduced, so that the gram capacity of the negative electrode material is reduced, and the energy density of the battery is reduced.
In a third aspect of the embodiments of the present application, a secondary battery is provided, in which a negative electrode sheet of the secondary battery contains the silicon composite negative electrode material described above, or contains the silicon composite negative electrode material prepared by the above method.
In the secondary battery provided by the third aspect of the embodiment of the present application, since the negative electrode plate includes the silicon composite negative electrode material, the silicon composite negative electrode material has excellent specific capacity, good structural stability and high ion electron transfer transmission efficiency, and thus, the electrochemical properties of the secondary battery, such as energy density, cycle life, safety, and the like, can be effectively improved.
In some embodiments, the negative electrode sheet of the secondary battery further includes components such as a binder and a conductive agent in addition to the silicon composite negative electrode material, and the materials are not particularly limited in this application embodiment, and suitable materials may be selected according to actual application requirements.
In some embodiments, the content of the binder in the active layer of the negative electrode sheet is 2 wt% to 4 wt%. In particular embodiments, the binder may be present in an amount of 2 wt%, 3 wt%, 4 wt%, and the like, which are typical and not limiting. In a specific embodiment, the binder comprises one or more of polyvinylidene chloride, soluble polytetrafluoroethylene, styrene butadiene rubber, hydroxypropyl methylcellulose, carboxymethylcellulose, polyvinyl alcohol, acrylonitrile copolymer, sodium alginate, chitosan, and chitosan derivatives.
In some embodiments, the content of the conductive agent in the active layer of the negative electrode sheet of the secondary battery is 3 wt% to 5 wt%. In specific embodiments, the content of the conductive agent may be 3 wt%, 4 wt%, 5 wt%, and the like, which are typical but not limiting contents. In particular embodiments, the conductive agent includes one or more of graphite, carbon black, acetylene black, graphene, carbon fibers, C60, and carbon nanotubes.
In some embodiments, the process of preparing the negative electrode sheet for the secondary battery may be: mixing the silicon composite negative electrode material, the conductive agent and the binder to obtain electrode slurry, coating the electrode slurry on a current collector, and drying, rolling, die cutting and the like to obtain the negative plate.
The secondary battery of the embodiment of the present application may be a lithium ion battery or a lithium metal battery.
The positive plate, the electrolyte, the diaphragm and the like of the secondary battery in the embodiment of the application are not particularly limited, and the secondary battery can be applied to any battery system.
In order to make the details and operations of the above-mentioned embodiments of the present invention clearly understood by those skilled in the art and to make the advanced performances of the silicon composite anode material, the preparation method thereof and the secondary battery of the embodiments of the present invention obviously manifest, the above-mentioned technical solutions are exemplified by a plurality of embodiments.
Example 1
A silicon composite anode material is prepared by the following steps:
weighing 2g of graphite flakes and 400mg of octadecylamine, weighing a certain amount of sec-butyl alcohol, putting the graphite flakes, the octadecylamine and the sec-butyl alcohol into a ball milling tank, carrying out ball milling at a rotating speed of 400r/min for 24 hours, separating ball milling products in different centrifugal intervals respectively to obtain graphene products in different centrifugal intervals, settling, centrifuging and washing the centrifugal products in different intervals, circulating for 4 times, and dispersing the final octadecylamine modified graphene product into the sec-butyl alcohol to form a dispersion liquid for later use.
② Cu (CH)3COO)2·H2O is dissolved in sec-butanol to form an organic solution, and the concentration of copper salt is 0.1 mol/L. Adding a surface modified octadecylamine graphene dispersion liquid, wherein the mass ratio of the surface modified octadecylamine graphene to copper is 1: 3. fully and uniformly stirring, and complexing the octadecylamine modified on the surface of the graphene and copper ions to form highly uniform and stable graphene-organic amine-copper complex dispersion liquid. Addition of acetaldehyde, acetaldehyde: the molar ratio of copper salt is about 0.5: under the action of acetaldehyde, Cu is reduced to form the copper-graphene-based composite material. In the process, the control of the reaction rate is realized by changing the quantity and the type of the organic amine on the surface of the graphene, for example, changing the length of an organic amine carbon chain, and the longer the carbon chain is, the slower the reaction is, so that the reduction rate is regulated and controlled. And finally, the obtained product is subjected to processes of centrifugation, washing and the like, and is circulated for 3 times, so that the copper-graphene-based composite material product is dispersed into sec-butyl alcohol to form a dispersion liquid, and the concentration is increased for later use.
Thirdly, soaking the micron silicon in the copper-graphene-based composite material dispersion liquid, uniformly mixing the micron silicon and the copper-graphene-based composite material dispersion liquid, performing ultrasonic dispersion on the mixture, and then drying the mixture in a vacuum freeze drying oven for 10 hours to obtain the micron silicon @ copper-graphene-based composite material, wherein the loading capacity of copper element is 23%.
Ball-milling and mixing the micron silicon @ copper-graphene-based composite material and a certain amount of amorphous carbon according to the mass ratio of 10:3 in a vibrating ball millAnd (5) 10 h. Then uniformly mixing the mixture, performing ultrasonic dispersion, and drying the mixture in a vacuum drying oven at the temperature of 50 ℃ for 12 hours. Then the ball-milled product is put into a tube furnace for chemical vapor deposition in Ar/H2Heating from room temperature to 500 ℃ at 6 ℃/min under inert atmosphere, followed by C2H2Chemical vapor deposition under Ar atmosphere for 50 minutes.
And fifthly, after chemical vapor deposition, cooling the product in a furnace, then adding the product into 1M hydrochloric acid solution for cleaning, then cleaning with 10% hydrofluoric acid, washing with water and ethanol for 4-5 times, and then drying in a vacuum oven to obtain the silicon composite negative electrode material of silicon @ copper-graphene @ amorphous carbon, wherein the particle size D50 of the silicon material core is 1um, the mass percentage content is 50%, the mass percentage content of the copper-graphene intermediate layer is 25%, and the mass percentage content of the amorphous carbon material outer shell layer is 25%.
A lithium ion battery prepared by the steps of:
preparing a negative plate: silicon @ copper-graphene @ amorphous carbon silicon composite negative electrode material: SBR as a binder: the conductive agent SP comprises the following components in percentage by mass: 2: 2, mixing and dissolving the mixture in a solvent to form uniformly dispersed and stable negative electrode slurry, coating the negative electrode slurry on a copper foil, putting the copper foil into an oven, drying the copper foil for 2 hours at 70 ℃, and compacting the copper foil by a roller press at the pressure of 9MPa to obtain a negative electrode sheet;
the electrolyte adopts 1M LiPF6And (EC: DMC ═ 1:1), preparing a button half cell by using a PE film as a diaphragm and a lithium sheet as a counter electrode in a glove box.
Example 2
A silicon composite anode material which is different from example 1 in that: and step three, in the micron silicon @ copper-graphene-based composite material prepared by the step three, the loading amount of copper element is 18%.
A lithium ion battery, which differs from the embodiments in that: the silicon composite negative electrode material of example 2 was used in the negative electrode sheet.
Example 3
A silicon composite anode material which is different from example 1 in that: in the silicon composite anode material of silicon @ copper-graphene @ amorphous carbon prepared in the fifth step, the particle size D50 of the silicon material core is 200nm, the mass percentage content is about 40%, the mass percentage content of the copper-graphene intermediate layer is about 30%, and the mass percentage content of the amorphous carbon material outer shell layer is about 30%.
A lithium ion battery, which differs from the embodiments in that: the silicon composite negative electrode material of example 3 was used in the negative electrode sheet.
Comparative example 1
A silicon composite anode material is prepared by the following steps:
soaking micron silicon in a graphene material dispersion liquid, wherein the mass ratio of the micron silicon to the graphene material dispersion liquid is 1: 0.5, uniformly mixing the materials, performing ultrasonic dispersion, and drying in a vacuum freeze drying oven for 10 hours to obtain the micron silicon @ graphene composite material.
And fourthly, ball-milling and mixing the micron silicon @ graphene composite material and a certain amount of amorphous carbon for 10 hours under a vibration ball mill according to the mass ratio of 10: 3. Then uniformly mixing the mixture, performing ultrasonic dispersion, and drying the mixture in a vacuum drying oven at the temperature of 50 ℃ for 12 hours. Then the ball-milled product is put into a tube furnace for chemical vapor deposition in Ar/H2Heating from room temperature to 500 ℃ at 6 ℃/min under inert atmosphere, followed by C2H2Chemical vapor deposition under Ar atmosphere for 50 minutes.
And fifthly, after chemical vapor deposition, cooling the product in a furnace, then adding the product into 1M hydrochloric acid solution for cleaning, then cleaning with 10% hydrofluoric acid, washing with water and ethanol for several cycles of 4-5 times, and then drying in a vacuum oven to obtain the silicon composite anode material of silicon @ graphene @ amorphous carbon, wherein the particle size D50 of the silicon material core is 200nm, the mass percentage content of the silicon material core is 42%, the mass percentage content of the graphene intermediate layer is 26%, and the mass percentage content of the amorphous carbon material outer shell layer is 32%.
A lithium ion battery, which differs from the embodiments in that: the silicon composite negative electrode material of comparative example 1 was used in the negative electrode sheet.
Further, in order to verify the advancement of the examples of the present application, the following battery performance tests were respectively performed for each of the examples and comparative examples:
the lithium ion batteries prepared in examples 1 to 5 and comparative example 1 were respectively discharged at 0.1C, charged to 2.5V at 0.1C, and the first lithium intercalation capacity and the first lithium deintercalation capacity were recorded and the first effect was calculated. In addition, the efficiency of each battery after 50 weeks of charge and discharge was measured. The test results are shown in table 1 below:
TABLE 1
Figure BDA0003295126070000161
From the test results, the silicon composite negative electrode materials with the core-shell structure of the silicon material core-copper graphene intermediate layer-amorphous carbon material outer shell layer prepared in embodiments 1 to 3 of the present application all show high capacity, high first efficiency, and high cycle stability. And the first effect and the cycling stability of the comparative example 1 with the middle layer only containing graphene are obviously lower than those of the examples 1-3.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (10)

1. The silicon composite negative electrode material is characterized in that the silicon composite negative electrode material is of a core-shell structure and comprises a silicon-based material core, and a middle layer and an outer shell which are sequentially coated on the outer surface of the core; wherein the intermediate layer comprises a carbon nanomaterial loaded with a metal element, and the outer shell layer comprises an amorphous carbon material.
2. The silicon composite anode material according to claim 1, wherein the metal element-loaded carbon nanomaterial includes: at least one of copper and silver;
and/or in the carbon nanomaterial loaded with the metal element, the carbon nanomaterial comprises: at least one of graphene and carbon nanotubes;
and/or the metal element-loaded carbon nanomaterial comprises 18-23 wt% of metal elements.
3. The silicon composite anode material according to claim 2, wherein the metal element-loaded carbon nanomaterial is selected from the group consisting of: copper-graphene composites.
4. The silicon composite anode material according to any one of claims 1 to 3, wherein the mass ratio of the silicon-based material core, the intermediate layer and the outer shell layer in the silicon composite anode material is 1: (0.5-0.8): (0.5 to 0.8);
and/or in the silicon composite negative electrode material, the particle size D50 of the silicon-based material core is 200 nm-1 μm, the thickness of the middle layer is 100 nm-1 μm, and the thickness of the outer shell layer is 100 nm-1 μm;
and/or, the silicon-based material is selected from: at least one of silicon simple substance, silicon oxide and silicon carbide.
5. The preparation method of the silicon composite anode material is characterized by comprising the following steps of:
preparing a carbon nano material loaded with metal elements;
obtaining a silicon-based material, and forming a coating middle layer on the surface of the silicon-based material by using the carbon nano material loaded with the metal element to obtain an intermediate product;
and preparing an outer shell layer of the amorphous carbon material on the outer surface of the intermediate product to obtain the silicon composite anode material.
6. The method for preparing a silicon composite anode material according to claim 5, wherein the step of preparing the carbon nanomaterial loaded with the metal element comprises: modifying the complexing agent on the surface of the carbon nanomaterial, complexing with metal salt, and reducing the metal salt to obtain the carbon nanomaterial loaded with metal elements;
and/or the step of forming the clad interlayer comprises: mixing the carbon nano material loaded with the metal element and the silicon-based material, and then drying in vacuum to obtain an intermediate product of which the middle layer is coated with the silicon-based material;
and/or the step of preparing the outer shell layer of amorphous carbon material comprises: and mixing the intermediate product with an amorphous carbon source, and performing vapor deposition to form an outer shell layer of the amorphous carbon material, thereby obtaining the silicon composite anode material.
7. The method of preparing a silicon composite anode material according to claim 6, wherein the complexing agent is selected from the group consisting of: at least one of octadecylamine, ethylenediamine, sec-butylamine, dodecylamine and hexadecylamine;
and/or, the metal salt is selected from: at least one of copper salt and silver salt;
and/or, the carbon nanomaterial is selected from: at least one of graphene and carbon nanotubes;
and/or, the amorphous carbon source is selected from: at least one of glucose, citric acid, asphalt, phenolic resin and epoxy resin;
and/or in the silicon composite negative electrode material, the mass ratio of the silicon-based material inner core to the middle layer to the outer shell layer is 1: (0.5-0.8): (0.5-0.8).
8. The method for preparing a silicon composite anode material according to claim 7, wherein the carbon nanomaterial loaded with a metal element is selected from a copper-graphene composite material, and the step of preparing the copper-graphene composite material comprises:
mixing and grinding the complexing agent and the graphene to obtain complexing agent modified graphene;
and dissolving the copper salt and the graphene modified by the complexing agent in an organic solvent, and adding a reducing agent to reduce the copper salt to obtain the copper-graphene composite material.
9. The method of preparing a silicon composite anode material according to claim 8, wherein the copper salt is selected from the group consisting of: cu (CH)3COO)2·H2At least one of O, copper sulfate, copper acetate and copper chloride;
and/or the mass ratio of the copper salt to the complexing agent-modified graphene is (0.01-2): 1;
and/or, the reducing agent is selected from: at least one of acetaldehyde, hydrazine hydrate, sodium borohydride, formaldehyde and propionaldehyde;
and/or, the organic solvent is selected from: at least one of sec-butyl alcohol, tert-butyl alcohol and ethanol.
10. A secondary battery, characterized in that the negative plate of the secondary battery comprises the silicon composite negative electrode material as defined in any one of claims 1 to 4 or the silicon composite negative electrode material prepared by the method as defined in any one of claims 5 to 9.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115050925A (en) * 2022-07-01 2022-09-13 山东仁丰特种材料股份有限公司 Electrode material, preparation method, electrode plate and battery

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116826059B (en) * 2023-08-29 2023-11-14 山东华太新能源电池有限公司 Lithium battery negative electrode material applied to marine environment and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105762351A (en) * 2016-05-04 2016-07-13 合肥工业大学 Lithium titanate/M-graphene composite cathode material for lithium ion battery and preparation method of lithium titanate/M-graphene composite cathode material
WO2019059438A1 (en) * 2017-09-25 2019-03-28 엠케이전자 주식회사 Secondary battery anode active material and manufacturing method therefor

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108539181A (en) * 2018-05-03 2018-09-14 东莞理工学院 A kind of lithium-ion negative pole composite material and preparation method
CN114864917A (en) * 2021-06-09 2022-08-05 江苏载驰科技股份有限公司 Silicon-carbon negative electrode material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105762351A (en) * 2016-05-04 2016-07-13 合肥工业大学 Lithium titanate/M-graphene composite cathode material for lithium ion battery and preparation method of lithium titanate/M-graphene composite cathode material
WO2019059438A1 (en) * 2017-09-25 2019-03-28 엠케이전자 주식회사 Secondary battery anode active material and manufacturing method therefor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115050925A (en) * 2022-07-01 2022-09-13 山东仁丰特种材料股份有限公司 Electrode material, preparation method, electrode plate and battery
CN115050925B (en) * 2022-07-01 2023-09-01 山东仁丰特种材料股份有限公司 Electrode material, preparation method, electrode plate and battery

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