WO2022126858A1 - Silicon-lithium battery and manufacturing method thereof - Google Patents

Silicon-lithium battery and manufacturing method thereof Download PDF

Info

Publication number
WO2022126858A1
WO2022126858A1 PCT/CN2021/077761 CN2021077761W WO2022126858A1 WO 2022126858 A1 WO2022126858 A1 WO 2022126858A1 CN 2021077761 W CN2021077761 W CN 2021077761W WO 2022126858 A1 WO2022126858 A1 WO 2022126858A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicon
lithium
separator
positive electrode
negative electrode
Prior art date
Application number
PCT/CN2021/077761
Other languages
French (fr)
Chinese (zh)
Inventor
朱少敏
刘春燕
Original Assignee
鹏盛国能(深圳)新能源集团有限公司
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 鹏盛国能(深圳)新能源集团有限公司 filed Critical 鹏盛国能(深圳)新能源集团有限公司
Publication of WO2022126858A1 publication Critical patent/WO2022126858A1/en

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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

Definitions

  • the invention relates to a silicon-lithium battery and a manufacturing method thereof, in particular to a safe silicon-lithium battery and a manufacturing method thereof.
  • silicon-lithium materials are regarded as key materials for high-energy electric vehicle power battery anodes.
  • the volume expansion of the silicon carbon anode material during the charging and discharging process of the battery will seriously affect the safety of the silicon-lithium battery, thus further restricting the application of the silicon carbon anode material in the power battery.
  • the purpose of the embodiments of the present invention is to provide a silicon-lithium battery and a manufacturing method thereof, which are used to solve the problem of low safety of the existing silicon-lithium battery.
  • An embodiment of the present invention discloses a silicon-lithium battery, comprising: a positive electrode, a negative electrode, an electrolyte and a separator, the electrolyte and the separator are interposed between the positive electrode and the negative electrode, and the positive electrode comprises lithium cobalt oxide nickel and lithium cobalt oxide oxide material, the separator comprises silicon germanium fibers, and the negative electrode is a silicon carbon composite material.
  • the separator is a polymer separator comprising silicon germanium fibers.
  • the silicon-carbon composite material comprises one or a combination of two or more of silicon nanoparticles, silicon nanowires or silicon nanotubes, and the silicon nanoparticles, silicon nanowires or silicon nanotubes are surrounded by porous carbon, amorphous Coated with carbon or graphite, the silicon-carbon composite material has a porous structure.
  • the electrolyte comprises one or a combination of two or more of sodium chloride, potassium chloride or calcium chloride.
  • the polymer separator has a porous structure, and the porous structure can only pass lithium ions.
  • the diameter of the silicon nanoparticles, silicon nanowires or silicon nanotubes is 20nm-200nm.
  • the positive electrode further includes tantalum oxide, and the mass proportion of the tantalum oxide is 0.1%-10%.
  • the duty ratio of the silicon carbon composite material is 1:2-1:3.
  • the embodiment of the present invention also discloses a method for manufacturing a lithium-silicon battery, comprising the steps of: S1: coating a negative electrode material, the negative electrode material being a silicon carbon composite material; S2: laying a separator, the separator comprising silicon germanium fibers; S3: Coating an electrolyte, the electrolyte comprising sodium halide; S4: coating a positive electrode material, the positive electrode material comprising lithium cobalt oxide nickel and lithium cobalt oxide.
  • step S5 is further included: controlling the liquid mass ratio in the silicon-lithium battery to 10%-0.01%.
  • the positive electrode of the silicon-lithium battery disclosed in the embodiment of the present invention comprises lithium cobalt oxide nickel and lithium cobalt acid oxide, and the negative electrode is a silicon-carbon composite material, so that the energy density of the silicon-lithium battery is higher.
  • the separator of the silicon-lithium battery uses silicon germanium.
  • the fiber is stronger than ordinary separators, which can effectively prevent lithium dendrites generated by lithium precipitation from piercing the separators, thereby significantly improving the safety of silicon-lithium batteries.
  • FIG. 1 is a schematic structural diagram of a silicon-lithium battery according to an embodiment of the present invention.
  • FIG. 2 is a schematic flowchart of a method for manufacturing a lithium-silicon battery according to another embodiment of the present invention.
  • FIG. 1 it is a schematic structural diagram of a silicon-lithium battery according to an embodiment of the present invention.
  • the silicon lithium battery 10 includes: a positive electrode 11, a negative electrode 12, an electrolyte 13 and a separator 14, the electrolyte 13 and the separator 14 are between the positive electrode 11 and the negative electrode 12, and the positive electrode 11 comprises lithium cobalt oxide nickel and Lithium cobalt oxide, the separator 14 includes silicon germanium fibers, and the negative electrode 12 is a silicon carbon composite material.
  • the electrolyte 13 is further dispersed in the gap of the positive electrode 11 .
  • the silicon-lithium battery 10 further includes a first current collector 18 and a second current collector 19 , the first current collector 18 is used for collecting the current of the positive electrode 11 , and the second current collector 19 is used for collecting the current of the negative electrode 12 .
  • the positive electrode 11 , the negative electrode 12 , the electrolyte 13 , the separator 14 , the first current collector 18 and the second current collector 19 are all sealed in a casing (not shown).
  • the mass ratio of lithium cobalt acid nickel and lithium cobalt acid oxide in the positive electrode 11 is 1:1, the positive electrode 11 includes a lithium cobalt acid nickel layer and a lithium cobalt acid oxide layer, and the lithium cobalt acid oxide is sprayed on.
  • the lithium cobalt oxide oxide layer is between the lithium nickel cobalt oxide layer and the separator 14, which is used to improve the corrosion resistance, high temperature resistance, oxidation resistance and other characteristics of the lithium nickel cobalt oxide layer. , which can greatly improve the service life of the battery and significantly increase the upper limit of the charging current.
  • the positive electrode 11 further includes tantalum oxide, and the tantalum oxide mass accounts for 0.1%-10%, which is used to increase the capacitance performance of the silicon-lithium battery 10 and improve the charging and discharging performance.
  • the charge stored in the tantalum oxide can be released instantaneously, and the response speed is much higher than the electrochemical reaction time of the lithium battery material, so that the discharge performance of the silicon lithium battery 10 is significantly higher than that of ordinary batteries.
  • the charge stored in the tantalum oxide is beneficial to maintain the stability and balance of the charging voltage, thereby significantly improving the charging performance of the lithium-silicon battery 10 .
  • the tantalum oxide layer is between the first current collector 18 and the positive electrode 11, and the tantalum oxide is uniformly sprayed on the first current collector 18 .
  • the mass proportion of the tantalum oxide is relatively high, for example, when the proportion is greater than 3% and less than or equal to 10%, the tantalum oxide is between the lithium cobalt oxide and the separator 14, and the tantalum oxide is between the lithium cobalt oxide and the separator 14. The oxide is uniformly sprayed on the surface of the lithium cobalt oxide or on the surface of the separator 14 close to the lithium cobalt oxide.
  • the negative electrode 12 is a silicon carbon composite material, and the silicon carbon composite material includes one or a combination of two or more of silicon nanoparticles, silicon nanowires or silicon nanotubes.
  • the silicon nanoparticles, silicon nanowires or silicon nanotubes The tube is covered with porous carbon, amorphous carbon or graphite, and the silicon-carbon composite material has a porous structure; the diameter of the silicon nanoparticle, silicon nanowire or silicon nanotube is 20nm-200nm;
  • the duty ratio is 1:1-1:3, the porous structure of the silicon-carbon composite material is used for accommodating the precipitated lithium crystals, and the size of the accommodation space formed by the porous structure of the silicon-carbon composite material is strongly related to the charge-discharge capacity.
  • the mass ratio of silicon nanoparticles to silicon nanowires or silicon nanotubes is 1:5-1:9
  • the silicon nanowires or silicon nanotubes are the main supporting materials for forming the porous structure
  • the silicon nanoparticles are auxiliary materials Supporting material, when the duty ratio of the silicon carbon composite material is 1:2, the comprehensive performance of the negative electrode 12 is the best.
  • the porous carbon, amorphous carbon or graphite coating the silicon nanoparticles, silicon nanowires or silicon nanotubes is used to prevent the silicon nanoparticles, silicon nanowires or silicon nanotubes from contacting the precipitated lithium crystals.
  • the electrolyte 13 includes one or a combination of two or more of sodium chloride, potassium chloride or calcium chloride. Wherein, when the electrolyte 13 adopts solid sodium halide, the problem of electrode corrosion can be effectively reduced.
  • the separator 14 is a polymer separator comprising silicon germanium fibers, and the polymer separator has a porous structure, and the porous structure can only pass lithium ions.
  • the separator 14 is stronger than ordinary polymer separators due to the addition of silicon germanium fibers, which can effectively prevent lithium dendrites generated by the precipitation of lithium crystals from piercing the separator 14, thereby making the silicon-lithium battery 10 significantly safer. improve.
  • the liquid mass ratio in the silicon-lithium battery 10 it is necessary to further control the liquid mass ratio in the silicon-lithium battery 10 to 10%-0.01%.
  • microwave heating, electric heating, etc. can be used to dry the liquid mass in the silicon-lithium battery 10.
  • the proportion is controlled within a specified range, so that the lithium-silicon battery 10 is in a semi-solid state, a quasi-solid state, or even an all-solid state, which can further improve the safety and stability of the lithium-silicon battery 10 .
  • FIG. 2 it is a schematic flowchart of a method for manufacturing a lithium-silicon battery according to another embodiment of the present invention.
  • a method for manufacturing a silicon-lithium battery comprising the steps of:
  • the silicon-carbon composite material comprises one or a combination of two or more of silicon nanoparticles, silicon nanowires or silicon nanotubes, and the silicon nanoparticles, silicon nanowires or silicon nanotubes are surrounded by porous carbon, amorphous carbon or graphite. Coating, the silicon-carbon composite material is in a porous structure; the diameter of the silicon nanoparticle, silicon nanowire or silicon nanotube is 20nm-200nm; the duty ratio of the silicon-carbon composite material is 1:1-1: 3.
  • the porous structure of the silicon-carbon composite material is used to accommodate the precipitated lithium crystals.
  • the overall performance of the negative electrode is the best.
  • the silicon carbon composite material is coated on the current collector.
  • the separator is a polymer separator comprising silicon germanium fibers, and the polymer separator has a porous structure. Preferably, the size of the porous structure can only pass lithium ions.
  • the separator is stronger than ordinary polymer separators because of the addition of silicon germanium fibers, which can effectively prevent lithium dendrites generated by lithium precipitation from piercing the separator, thereby significantly improving the safety of the silicon-lithium battery.
  • the mass ratio of lithium cobalt acid nickel and lithium cobalt acid oxide in the positive electrode material is 1:1, the positive electrode material includes a lithium cobalt acid nickel layer and a lithium cobalt acid oxide layer, and the lithium cobalt acid oxide is sprayed on On the surface of lithium nickel cobalt oxide, the lithium cobalt oxide oxide layer is between the lithium nickel cobalt oxide layer and the separator, which is used to improve the corrosion resistance, high temperature resistance, oxidation resistance and other characteristics of the lithium nickel cobalt oxide layer, which can greatly improve the battery service life and significantly increase the upper limit of charging current.
  • the positive electrode material may further include tantalum oxide, and the mass proportion of the tantalum oxide is 0.1%-10%, which is used to increase the capacitance of the silicon-lithium battery and improve the charging and discharging performance.
  • the step S4: coating the positive electrode material can be performed simultaneously with the step S1: coating the negative electrode material, and then the positive electrode material, electrolyte, separator and negative electrode material are pressed together.
  • the steps S1 , S2 , S3 and S4 can be flexibly set in sequence or performed synchronously according to different production processes.
  • the electrolyte is conveniently coated as a mixture of a solvent and sodium halide powder, and the solvent can be a trace amount of water or a volatile solvent, and has no adverse reaction with the positive electrode, the negative electrode and the separator during manufacture.
  • the electrolyte can be directly coated on the surface of the positive electrode material, or coated on other media, and then transported between the positive electrode and the separator.
  • the step S5 control the liquid mass ratio in the silicon-lithium battery to 10%-0.01%, specifically by microwave heating, electric heating, etc. drying, and control the liquid mass ratio in the silicon-lithium battery to be within the range of 10%-0.01%.
  • the silicon lithium battery is made to be in a semi-solid state, a quasi-solid state, or even an all-solid state. Due to the strict control of the liquid quality in the lithium-silicon battery, even when the separator is damaged, the direct reaction between the positive electrode and the negative electrode can be effectively reduced due to the lack of a medium. The safety and stability of the battery.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Provided is a silicon-lithium battery, comprising a positive electrode (11), a negative electrode (12), an electrolyte (13) and a separator (14), wherein the electrolyte (13) and the separator (14) are arranged between the positive electrode (11) and the negative electrode (12); the positive electrode (11) comprises lithium nickel cobaltate and lithium cobaltate oxide; the separator (14) comprises silicon-germanium fibers; and the negative electrode (12) is a silicon-carbon composite material. The positive electrode (11) of the silicon-lithium battery comprises lithium nickel cobaltate and lithium cobaltate oxide, and the negative electrode (12) is a silicon-carbon composite material, such that the energy density of the silicon-lithium battery is relatively high; in addition, the separator (14) of the silicon-lithium battery is made of silicon-germanium fibers, which makes it stronger than an ordinary separator, and lithium dendrites generated by lithium precipitation can be effectively prevented from piercing the separator, thereby significantly improving the safety of the silicon-lithium battery.

Description

一种硅锂电池及其制造方法A kind of silicon lithium battery and its manufacturing method 技术领域technical field
本发明涉及一种硅锂电池及其制造方法，特别是涉及一种安全硅锂电池及其制造方法。The invention relates to a silicon-lithium battery and a manufacturing method thereof, in particular to a safe silicon-lithium battery and a manufacturing method thereof.
背景技术Background technique
目前随着全球新能源汽车产业的快速发展，新能源产业也得到蓬勃发展。从目前国内新能源汽车产业来看，发展电动车是环境保护和产业升级的必然趋势。随着电动汽车销售量越来越大，动力电池的需求也越来越大，同时对动力电池的容量、电压以及使用寿命都提出了更高的要求。At present, with the rapid development of the global new energy vehicle industry, the new energy industry is also booming. Judging from the current domestic new energy vehicle industry, the development of electric vehicles is an inevitable trend in environmental protection and industrial upgrading. With the increasing sales of electric vehicles, the demand for power batteries is also increasing, and higher requirements are placed on the capacity, voltage and service life of power batteries.
硅锂材料由于能量密度较高，被视为用于高能量电动车动力电池负极的关键材料。硅碳负极材料在电池充放电过程中伴随着的体积膨胀，会严重影响硅锂电池的安全性，从而使得硅碳负极材料在动力电池中的应用受到进一步的限制。Due to its high energy density, silicon-lithium materials are regarded as key materials for high-energy electric vehicle power battery anodes. The volume expansion of the silicon carbon anode material during the charging and discharging process of the battery will seriously affect the safety of the silicon-lithium battery, thus further restricting the application of the silicon carbon anode material in the power battery.
发明内容SUMMARY OF THE INVENTION
本发明实施例目的旨在提供一种硅锂电池及其制造方法，用于解决现有的硅锂电池安全性较低的问题。The purpose of the embodiments of the present invention is to provide a silicon-lithium battery and a manufacturing method thereof, which are used to solve the problem of low safety of the existing silicon-lithium battery.
本发明实施例公开了一种硅锂电池，包括：正极、负极、电解质和隔膜，所述电解质和隔膜介于所述正极和负极之间，所述正极包含锂钴酸镍和锂钴酸氧化物，所述隔膜包含硅锗纤维，所述负极为硅碳复合材料。An embodiment of the present invention discloses a silicon-lithium battery, comprising: a positive electrode, a negative electrode, an electrolyte and a separator, the electrolyte and the separator are interposed between the positive electrode and the negative electrode, and the positive electrode comprises lithium cobalt oxide nickel and lithium cobalt oxide oxide material, the separator comprises silicon germanium fibers, and the negative electrode is a silicon carbon composite material.
优选的，所述隔膜为包含硅锗纤维聚合物隔膜。Preferably, the separator is a polymer separator comprising silicon germanium fibers.
优选的，所述硅碳复合材料包含硅纳米颗粒、硅纳米线或硅纳米管中一种或两种以上的组合，所述硅纳米颗粒、硅纳米线或硅纳米管被多孔碳、 无定型碳或石墨包覆，所述硅碳复合材料呈多孔结构。Preferably, the silicon-carbon composite material comprises one or a combination of two or more of silicon nanoparticles, silicon nanowires or silicon nanotubes, and the silicon nanoparticles, silicon nanowires or silicon nanotubes are surrounded by porous carbon, amorphous Coated with carbon or graphite, the silicon-carbon composite material has a porous structure.
优选的，所述电解质包含氯化钠、氯化钾或氯化钙中一种或两种以上的组合。Preferably, the electrolyte comprises one or a combination of two or more of sodium chloride, potassium chloride or calcium chloride.
优选的，所述聚合物隔膜为多孔结构，所述多孔结构仅可通过锂离子。Preferably, the polymer separator has a porous structure, and the porous structure can only pass lithium ions.
优选的，所述硅纳米颗粒、硅纳米线或硅纳米管的直径为20nm-200nm。Preferably, the diameter of the silicon nanoparticles, silicon nanowires or silicon nanotubes is 20nm-200nm.
优选的，所述正极进一步包括钽氧化物，所述钽氧化物质量占比0.1％-10％。Preferably, the positive electrode further includes tantalum oxide, and the mass proportion of the tantalum oxide is 0.1%-10%.
优选的，所述硅碳复合材料的占空比为1:2-1:3。Preferably, the duty ratio of the silicon carbon composite material is 1:2-1:3.
本发明实施例还公开了一种硅锂电池制造方法，包括步骤：S1：涂覆负极材料，所述负极材料为硅碳复合材料；S2：铺设隔膜，所述隔膜包含硅锗纤维；S3：涂覆电解质，所述电解质包含卤化钠；S4：涂覆正极材料，所述正极材料包含锂钴酸镍和锂钴酸氧化物。The embodiment of the present invention also discloses a method for manufacturing a lithium-silicon battery, comprising the steps of: S1: coating a negative electrode material, the negative electrode material being a silicon carbon composite material; S2: laying a separator, the separator comprising silicon germanium fibers; S3: Coating an electrolyte, the electrolyte comprising sodium halide; S4: coating a positive electrode material, the positive electrode material comprising lithium cobalt oxide nickel and lithium cobalt oxide.
优选的，进一步包括步骤S5：将硅锂电池中的液体质量占比控制在10％-0.01％。Preferably, step S5 is further included: controlling the liquid mass ratio in the silicon-lithium battery to 10%-0.01%.
本发明实施例公开的硅锂电池正极包含锂钴酸镍和锂钴酸氧化物，负极为硅碳复合材料，使得硅锂电池的能量密度较高，同时，硅锂电池的隔膜使用了硅锗纤维，使得比普通隔膜更加强韧，可以有效避免锂析出产生的锂枝晶刺穿隔膜，从而使得硅锂电池的安全性显著提高。The positive electrode of the silicon-lithium battery disclosed in the embodiment of the present invention comprises lithium cobalt oxide nickel and lithium cobalt acid oxide, and the negative electrode is a silicon-carbon composite material, so that the energy density of the silicon-lithium battery is higher. Meanwhile, the separator of the silicon-lithium battery uses silicon germanium. The fiber is stronger than ordinary separators, which can effectively prevent lithium dendrites generated by lithium precipitation from piercing the separators, thereby significantly improving the safety of silicon-lithium batteries.
附图说明Description of drawings
图1为本发明的一个实施例的硅锂电池结构示意图；1 is a schematic structural diagram of a silicon-lithium battery according to an embodiment of the present invention;
图2为本发明的另一个实施例的硅锂电池制造方法流程示意图。FIG. 2 is a schematic flowchart of a method for manufacturing a lithium-silicon battery according to another embodiment of the present invention.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体 实施例仅用以解释本发明，并不用于限定本发明。In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.
如图1所示，为本发明的一个实施例的硅锂电池结构示意图。所述一种硅锂电池10，包括：正极11、负极12、电解质13和隔膜14，所述电解质13和隔膜14介于正极11和负极12之间，所述正极11包含锂钴酸镍和锂钴酸氧化物，所述隔膜14包含硅锗纤维，所述负极12为硅碳复合材料。所述电解质13进一步散布在正极11间隙中。所述一种硅锂电池10进一步包括第一集流体18和第二集流体19，所述第一集流体18用于汇集正极11电流，所述第二集流体19用于汇集负极12电流。所述正极11、负极12、电解质13、隔膜14、第一集流体18和第二集流体19皆密封置于壳体(图未示)内。As shown in FIG. 1 , it is a schematic structural diagram of a silicon-lithium battery according to an embodiment of the present invention. The silicon lithium battery 10 includes: a positive electrode 11, a negative electrode 12, an electrolyte 13 and a separator 14, the electrolyte 13 and the separator 14 are between the positive electrode 11 and the negative electrode 12, and the positive electrode 11 comprises lithium cobalt oxide nickel and Lithium cobalt oxide, the separator 14 includes silicon germanium fibers, and the negative electrode 12 is a silicon carbon composite material. The electrolyte 13 is further dispersed in the gap of the positive electrode 11 . The silicon-lithium battery 10 further includes a first current collector 18 and a second current collector 19 , the first current collector 18 is used for collecting the current of the positive electrode 11 , and the second current collector 19 is used for collecting the current of the negative electrode 12 . The positive electrode 11 , the negative electrode 12 , the electrolyte 13 , the separator 14 , the first current collector 18 and the second current collector 19 are all sealed in a casing (not shown).
所述正极11中锂钴酸镍和锂钴酸氧化物的质量比为1:1，所述正极11包括锂钴酸镍层和锂钴酸氧化物层，所述锂钴酸氧化物喷涂在锂钴酸镍表面，所述锂钴酸氧化物层介于所述锂钴酸镍层和所述隔膜14之间，用于提高锂钴酸镍层的耐腐蚀、耐高温、抗氧化等特性，可以大幅提高电池的使用寿命，并显著提高充电电流上限。其中，所述正极11进一步包括钽氧化物，所述钽氧化物质量占比0.1％-10％，用于增加所述硅锂电池10的电容性能，提高充放电性能。在放电时，存储在钽氧化物中的电荷可以瞬间放出，响应速度远高于锂电池材料电化学反应时间，从而使得硅锂电池10的放电性能显著高于普通电池。在充电时，存储在钽氧化物中的电荷有利于维持充电电压的稳定性和均衡性，从而使得硅锂电池10的充电性能显著提高。当所述钽氧化物质量占比较低时，比如占比0.1％-3％时，钽氧化物层介于所述第一集流体18和所述正极11之间，所述钽氧化物均匀喷涂在所述第一集流体18上。当所述钽氧化物质量占比较高时，比如占比大于3％，小于等于10％时，所述钽氧化物介于所述锂钴酸氧化物和所述隔膜14之间，所述钽氧化物均匀喷涂在所述锂钴酸氧化物表面或者喷涂在所述隔膜14靠近所述锂钴酸氧化物表面。The mass ratio of lithium cobalt acid nickel and lithium cobalt acid oxide in the positive electrode 11 is 1:1, the positive electrode 11 includes a lithium cobalt acid nickel layer and a lithium cobalt acid oxide layer, and the lithium cobalt acid oxide is sprayed on. On the surface of lithium nickel cobalt oxide, the lithium cobalt oxide oxide layer is between the lithium nickel cobalt oxide layer and the separator 14, which is used to improve the corrosion resistance, high temperature resistance, oxidation resistance and other characteristics of the lithium nickel cobalt oxide layer. , which can greatly improve the service life of the battery and significantly increase the upper limit of the charging current. Wherein, the positive electrode 11 further includes tantalum oxide, and the tantalum oxide mass accounts for 0.1%-10%, which is used to increase the capacitance performance of the silicon-lithium battery 10 and improve the charging and discharging performance. During discharge, the charge stored in the tantalum oxide can be released instantaneously, and the response speed is much higher than the electrochemical reaction time of the lithium battery material, so that the discharge performance of the silicon lithium battery 10 is significantly higher than that of ordinary batteries. During charging, the charge stored in the tantalum oxide is beneficial to maintain the stability and balance of the charging voltage, thereby significantly improving the charging performance of the lithium-silicon battery 10 . When the mass proportion of the tantalum oxide is relatively low, such as 0.1%-3%, the tantalum oxide layer is between the first current collector 18 and the positive electrode 11, and the tantalum oxide is uniformly sprayed on the first current collector 18 . When the mass proportion of the tantalum oxide is relatively high, for example, when the proportion is greater than 3% and less than or equal to 10%, the tantalum oxide is between the lithium cobalt oxide and the separator 14, and the tantalum oxide is between the lithium cobalt oxide and the separator 14. The oxide is uniformly sprayed on the surface of the lithium cobalt oxide or on the surface of the separator 14 close to the lithium cobalt oxide.
所述负极12为硅碳复合材料，所述硅碳复合材料包含硅纳米颗粒、硅纳米线或硅纳米管中一种或两种以上的组合，所述硅纳米颗粒、硅纳米线或硅纳米管被多孔碳、无定型碳或石墨包覆，所述硅碳复合材料呈多孔结构；所述硅纳米颗粒、硅纳米线或硅纳米管的直径为20nm-200nm；所述硅碳复合材料的占空比为1:1-1:3，所述硅碳复合材料的多孔结构用于容置析出的锂晶，所述硅碳复合材料多孔结构形成容置空间大小与充放电容量强相关。其中，硅纳米颗粒与硅纳米线或硅纳米管的质量比为1:5-1:9，所述硅纳米线或硅纳米管为形成多孔结构的主要支撑材料，所述硅纳米颗粒为辅助支撑材料，所述硅碳复合材料的占空比为1:2时，所述负极12的综合性能最佳。所述多孔碳、无定型碳或石墨包覆所述硅纳米颗粒、硅纳米线或硅纳米管用于避免所述所述硅纳米颗粒、硅纳米线或硅纳米管与析出的锂晶接触。The negative electrode 12 is a silicon carbon composite material, and the silicon carbon composite material includes one or a combination of two or more of silicon nanoparticles, silicon nanowires or silicon nanotubes. The silicon nanoparticles, silicon nanowires or silicon nanotubes The tube is covered with porous carbon, amorphous carbon or graphite, and the silicon-carbon composite material has a porous structure; the diameter of the silicon nanoparticle, silicon nanowire or silicon nanotube is 20nm-200nm; The duty ratio is 1:1-1:3, the porous structure of the silicon-carbon composite material is used for accommodating the precipitated lithium crystals, and the size of the accommodation space formed by the porous structure of the silicon-carbon composite material is strongly related to the charge-discharge capacity. Wherein, the mass ratio of silicon nanoparticles to silicon nanowires or silicon nanotubes is 1:5-1:9, the silicon nanowires or silicon nanotubes are the main supporting materials for forming the porous structure, and the silicon nanoparticles are auxiliary materials Supporting material, when the duty ratio of the silicon carbon composite material is 1:2, the comprehensive performance of the negative electrode 12 is the best. The porous carbon, amorphous carbon or graphite coating the silicon nanoparticles, silicon nanowires or silicon nanotubes is used to prevent the silicon nanoparticles, silicon nanowires or silicon nanotubes from contacting the precipitated lithium crystals.
所述电解质13包含氯化钠、氯化钾或氯化钙中一种或两种以上的组合。其中，所述电解质13采用固态卤化钠时，可以有效减少电极腐蚀的问题发生。The electrolyte 13 includes one or a combination of two or more of sodium chloride, potassium chloride or calcium chloride. Wherein, when the electrolyte 13 adopts solid sodium halide, the problem of electrode corrosion can be effectively reduced.
所述隔膜14为包含硅锗纤维聚合物隔膜，所述聚合物隔膜为多孔结构，所述多孔结构仅可通过锂离子。所述隔膜14因为添加了硅锗纤维，使得比普通聚合物隔膜更加强韧，可以有效避免锂晶析出产生的锂枝晶刺穿所述隔膜14，从而使得所述硅锂电池10安全性显著提高。The separator 14 is a polymer separator comprising silicon germanium fibers, and the polymer separator has a porous structure, and the porous structure can only pass lithium ions. The separator 14 is stronger than ordinary polymer separators due to the addition of silicon germanium fibers, which can effectively prevent lithium dendrites generated by the precipitation of lithium crystals from piercing the separator 14, thereby making the silicon-lithium battery 10 significantly safer. improve.
优选的，需要进一步将所述硅锂电池10中的液体质量占比控制在10％-0.01％，具体可通过微波加热、电加热等方式烘干，将所述硅锂电池10中的液体质量占比控制在指定范围内，使得所述硅锂电池10处于半固态、准固态，甚至全固态状态，可以进一步提高所述硅锂电池10的安全性和稳定性。Preferably, it is necessary to further control the liquid mass ratio in the silicon-lithium battery 10 to 10%-0.01%. Specifically, microwave heating, electric heating, etc. can be used to dry the liquid mass in the silicon-lithium battery 10. The proportion is controlled within a specified range, so that the lithium-silicon battery 10 is in a semi-solid state, a quasi-solid state, or even an all-solid state, which can further improve the safety and stability of the lithium-silicon battery 10 .
如图2所示，为本发明的另一个实施例的硅锂电池制造方法流程示意 图。一种硅锂电池制造方法，包括步骤：As shown in FIG. 2 , it is a schematic flowchart of a method for manufacturing a lithium-silicon battery according to another embodiment of the present invention. A method for manufacturing a silicon-lithium battery, comprising the steps of:
S1：涂覆负极材料，所述负极材料为硅碳复合材料；S1: coating a negative electrode material, the negative electrode material is a silicon carbon composite material;
S2：铺设隔膜，所述隔膜包含硅锗纤维；S2: laying a diaphragm, the diaphragm comprising silicon germanium fibers;
S3：涂覆电解质，所述电解质包含卤化钠；S3: coating an electrolyte, the electrolyte comprising sodium halide;
S4：涂覆正极材料，所述正极材料包含锂钴酸镍和锂钴酸氧化物。S4: Coating a positive electrode material, the positive electrode material comprising lithium cobalt oxide nickel and lithium cobalt oxide.
S5：将硅锂电池中的液体质量占比控制在10％-0.01％。S5: Control the liquid mass ratio in the silicon-lithium battery to 10%-0.01%.
所述硅碳复合材料包含硅纳米颗粒、硅纳米线或硅纳米管中一种或两种以上的组合，所述硅纳米颗粒、硅纳米线或硅纳米管被多孔碳、无定型碳或石墨包覆，所述硅碳复合材料呈多孔结构；所述硅纳米颗粒、硅纳米线或硅纳米管的直径为20nm-200nm；所述硅碳复合材料的占空比为1:1-1:3，所述硅碳复合材料的多孔结构用于容置析出的锂晶。其中，硅纳米颗粒与硅纳米线或硅纳米管的质量比为1:5-1:9，所述硅碳复合材料的占空比为1:2时，所述负极的综合性能最佳。优选的，所述硅碳复合材料涂覆在集流体上。The silicon-carbon composite material comprises one or a combination of two or more of silicon nanoparticles, silicon nanowires or silicon nanotubes, and the silicon nanoparticles, silicon nanowires or silicon nanotubes are surrounded by porous carbon, amorphous carbon or graphite. Coating, the silicon-carbon composite material is in a porous structure; the diameter of the silicon nanoparticle, silicon nanowire or silicon nanotube is 20nm-200nm; the duty ratio of the silicon-carbon composite material is 1:1-1: 3. The porous structure of the silicon-carbon composite material is used to accommodate the precipitated lithium crystals. Wherein, when the mass ratio of silicon nanoparticles to silicon nanowires or silicon nanotubes is 1:5-1:9, and the duty ratio of the silicon-carbon composite material is 1:2, the overall performance of the negative electrode is the best. Preferably, the silicon carbon composite material is coated on the current collector.
所述隔膜为包含硅锗纤维聚合物隔膜，所述聚合物隔膜为多孔结构，优选的，所述多孔结构大小仅可通过锂离子。所述隔膜因为添加了硅锗纤维，使得比普通聚合物隔膜更加强韧，可以有效避免锂析出产生的锂枝晶刺穿所述隔膜，从而使得所述硅锂电池安全性显著提高。The separator is a polymer separator comprising silicon germanium fibers, and the polymer separator has a porous structure. Preferably, the size of the porous structure can only pass lithium ions. The separator is stronger than ordinary polymer separators because of the addition of silicon germanium fibers, which can effectively prevent lithium dendrites generated by lithium precipitation from piercing the separator, thereby significantly improving the safety of the silicon-lithium battery.
所述正极材料中锂钴酸镍和锂钴酸氧化物的质量比为1:1，所述正极材料包括锂钴酸镍层和锂钴酸氧化物层，所述锂钴酸氧化物喷涂在锂钴酸镍表面，所述锂钴酸氧化物层介于锂钴酸镍层和隔膜之间，用于提高锂钴酸镍层的耐腐蚀、耐高温、抗氧化等特性，可以大幅提高电池的使用寿命，并显著提高充电电流上限。其中，所述正极材料可以进一步包括钽氧化物，所述钽氧化物质量占比0.1％-10％，用于增加所述硅锂电池的电容，提高充放电性能。优选的，根据硅锂电池生产工艺设计，所述步骤S4：涂覆正极材料，可以与步骤S1：涂覆负极材料同步进行，然后将正极材料、电解质、 隔膜和负极材料压合到一起。所述步骤S1、S2、S3和S4可以根据不同生产工艺灵活设置先后顺序或同步进行。The mass ratio of lithium cobalt acid nickel and lithium cobalt acid oxide in the positive electrode material is 1:1, the positive electrode material includes a lithium cobalt acid nickel layer and a lithium cobalt acid oxide layer, and the lithium cobalt acid oxide is sprayed on On the surface of lithium nickel cobalt oxide, the lithium cobalt oxide oxide layer is between the lithium nickel cobalt oxide layer and the separator, which is used to improve the corrosion resistance, high temperature resistance, oxidation resistance and other characteristics of the lithium nickel cobalt oxide layer, which can greatly improve the battery service life and significantly increase the upper limit of charging current. Wherein, the positive electrode material may further include tantalum oxide, and the mass proportion of the tantalum oxide is 0.1%-10%, which is used to increase the capacitance of the silicon-lithium battery and improve the charging and discharging performance. Preferably, according to the production process design of the silicon-lithium battery, the step S4: coating the positive electrode material can be performed simultaneously with the step S1: coating the negative electrode material, and then the positive electrode material, electrolyte, separator and negative electrode material are pressed together. The steps S1 , S2 , S3 and S4 can be flexibly set in sequence or performed synchronously according to different production processes.
所述电解质为方便涂覆为溶剂加卤化钠粉末的混合物，所述溶剂可以为微量的水或者易挥发性溶剂，且制造时与正极、负极和隔膜无不良反应。所述电解质可以直接涂覆在正极材料表面，或者涂覆在其他介质上，再转运到正极与隔膜之间。The electrolyte is conveniently coated as a mixture of a solvent and sodium halide powder, and the solvent can be a trace amount of water or a volatile solvent, and has no adverse reaction with the positive electrode, the negative electrode and the separator during manufacture. The electrolyte can be directly coated on the surface of the positive electrode material, or coated on other media, and then transported between the positive electrode and the separator.
所述步骤S5：将硅锂电池中的液体质量占比控制在10％-0.01％，具体可通过微波加热、电加热等方式烘干，将所述硅锂电池中的液体质量占比控制在指定范围内，使得所述硅锂电池处于半固态、准固态，甚至全固态状态。由于硅锂电池中液体质量的严格控制，即使隔膜发生破损时，由于缺少媒介，也可以有效减少正极与负极直接反应，比如发生电池穿刺或严重形变时导致隔膜破损，可以进一步提高所述硅锂电池的安全性和稳定性。The step S5: control the liquid mass ratio in the silicon-lithium battery to 10%-0.01%, specifically by microwave heating, electric heating, etc. drying, and control the liquid mass ratio in the silicon-lithium battery to be within the range of 10%-0.01%. Within the specified range, the silicon lithium battery is made to be in a semi-solid state, a quasi-solid state, or even an all-solid state. Due to the strict control of the liquid quality in the lithium-silicon battery, even when the separator is damaged, the direct reaction between the positive electrode and the negative electrode can be effectively reduced due to the lack of a medium. The safety and stability of the battery.
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；在本发明的思路下，以上实施例或者不同实施例中的技术特征之间也可以进行组合，并存在如上的本发明的不同方面的许多其它变化，为了简明，它们没有在细节中提供。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; under the idea of the present invention, the technical features in the above embodiments or different embodiments can also be combined, And there are many other variations of the various aspects of the invention as above, which have not been provided in detail for the sake of brevity.

Claims (10)

  1. 一种硅锂电池，包括：正极、负极、电解质和隔膜，所述电解质和所述隔膜介于所述正极和负极之间，其特征在于：所述正极包含锂钴酸镍和锂钴酸氧化物，所述隔膜包含硅锗纤维，所述负极为硅碳复合材料。A silicon-lithium battery, comprising: a positive electrode, a negative electrode, an electrolyte and a separator, wherein the electrolyte and the separator are between the positive electrode and the negative electrode, and characterized in that: the positive electrode comprises lithium cobalt oxide nickel and lithium cobalt oxide oxide material, the separator comprises silicon germanium fibers, and the negative electrode is a silicon carbon composite material.
  2. 根据权利要求1所述的硅锂电池，其特征在于：所述隔膜为包含硅锗纤维聚合物隔膜。The lithium-silicon battery according to claim 1, wherein the separator is a polymer separator comprising silicon germanium fibers.
  3. 根据权利要求1所述的硅锂电池，其特征在于：所述硅碳复合材料包含硅纳米颗粒、硅纳米线或硅纳米管中一种或两种以上的组合，所述硅纳米颗粒、硅纳米线或硅纳米管被多孔碳、无定型碳或石墨包覆，所述硅碳复合材料呈多孔结构。The lithium-silicon battery according to claim 1, wherein the silicon-carbon composite material comprises one or a combination of two or more of silicon nanoparticles, silicon nanowires or silicon nanotubes, and the silicon nanoparticles, silicon Nanowires or silicon nanotubes are coated with porous carbon, amorphous carbon or graphite, and the silicon-carbon composite material has a porous structure.
  4. 根据权利要求1所述的硅锂电池，其特征在于：所述电解质包含氯化钠、氯化钾或氯化钙中一种或两种以上的组合。The lithium-silicon battery according to claim 1, wherein the electrolyte comprises one or a combination of two or more of sodium chloride, potassium chloride or calcium chloride.
  5. 根据权利要求2所述的硅锂电池，其特征在于：所述聚合物隔膜为多孔结构，所述多孔结构仅可通过锂离子。The lithium-silicon battery according to claim 2, wherein the polymer separator has a porous structure, and the porous structure can only pass lithium ions.
  6. 根据权利要求3所述的硅锂电池，其特征在于：所述硅纳米颗粒、硅纳米线或硅纳米管的直径为20nm-200nm。The lithium-silicon battery according to claim 3, wherein the diameter of the silicon nanoparticles, silicon nanowires or silicon nanotubes is 20nm-200nm.
  7. 根据权利要求1所述的硅锂电池，其特征在于：所述正极进一步包括钽氧化物，所述钽氧化物质量占比0.1％-10％。The lithium-silicon battery according to claim 1, wherein the positive electrode further comprises tantalum oxide, and the mass proportion of the tantalum oxide is 0.1%-10%.
  8. 根据权利要求3所述的硅锂电池，其特征在于：所述硅碳复合材料的占空比为1:2-1:3。The silicon-lithium battery according to claim 3, wherein the duty ratio of the silicon-carbon composite material is 1:2-1:3.
  9. 一种硅锂电池制造方法，其特征在于包括步骤：A method for manufacturing a lithium-silicon battery, comprising the steps of:
    S1：涂覆负极材料，所述负极材料为硅碳复合材料；S1: coating a negative electrode material, the negative electrode material is a silicon carbon composite material;
    S2：铺设隔膜，所述隔膜包含硅锗纤维；S2: laying a diaphragm, the diaphragm comprising silicon germanium fibers;
    S3：涂覆电解质，所述电解质包含卤化钠；S3: coating an electrolyte, the electrolyte comprising sodium halide;
    S4：涂覆正极材料，所述正极材料包含锂钴酸镍和锂钴酸氧化物。S4: Coating a positive electrode material, the positive electrode material comprising lithium cobalt oxide nickel and lithium cobalt oxide.
  10. 根据权利要求9所述的硅锂电池制造方法，其特征在于进一步包 括步骤S5：将硅锂电池中的液体质量占比控制在10％-0.01％。The method for manufacturing a lithium-silicon battery according to claim 9, further comprising step S5: controlling the liquid mass ratio in the lithium-silicon battery to 10%-0.01%.
PCT/CN2021/077761 2020-12-14 2021-02-25 Silicon-lithium battery and manufacturing method thereof WO2022126858A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011468261.8A CN112490431A (en) 2020-12-14 2020-12-14 Silicon lithium battery and manufacturing method thereof
CN202011468261.8 2020-12-14

Publications (1)

Publication Number Publication Date
WO2022126858A1 true WO2022126858A1 (en) 2022-06-23

Family

ID=74918088

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/077761 WO2022126858A1 (en) 2020-12-14 2021-02-25 Silicon-lithium battery and manufacturing method thereof

Country Status (2)

Country Link
CN (1) CN112490431A (en)
WO (1) WO2022126858A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113506909B (en) * 2021-05-07 2022-07-26 鹏盛国能(深圳)新能源集团有限公司 Lithium battery and electrolyte thereof
CN113506869A (en) * 2021-05-07 2021-10-15 鹏盛国能(深圳)新能源集团有限公司 Lithium battery and anode thereof
CN114709491B (en) * 2022-06-06 2022-08-16 深圳鑫鹏能技术科技有限公司 High-density silicon lithium tantalum battery and manufacturing process method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1387270A (en) * 2002-06-28 2002-12-25 南开大学 Process for preparing positive electrode material for secondary Li-ion battery
WO2016176928A1 (en) * 2015-05-06 2016-11-10 南开大学 Negative electrode material, preparation method therefor, and lithium-ion secondary battery using the negative electrode material
CN107240672A (en) * 2017-05-08 2017-10-10 禾畚兴业有限公司 A kind of method for adding graphene in the positive and negative pole plate of lithium battery
WO2017190364A1 (en) * 2016-05-06 2017-11-09 深圳先进技术研究院 Secondary battery and preparation method therefor
CN107611356A (en) * 2017-07-18 2018-01-19 深圳市沃特玛电池有限公司 A kind of silicon-carbon cathode lithium ion battery
CN108808073A (en) * 2018-06-29 2018-11-13 深圳鑫鹏能技术科技有限公司 A kind of silicon lithium tantalum capacitor batteries

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090125256A (en) * 2007-03-26 2009-12-04 사임베트 코퍼레이션 Substrate for lithium thin film battery
US9627670B2 (en) * 2013-07-31 2017-04-18 Infineon Technologies Ag Battery cell and method for making battery cell
CN111653702B (en) * 2020-06-11 2021-02-05 鹏盛国能(深圳)新能源集团有限公司 Full-oxide solid silicon-carbon-lithium-tantalum battery structure

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1387270A (en) * 2002-06-28 2002-12-25 南开大学 Process for preparing positive electrode material for secondary Li-ion battery
WO2016176928A1 (en) * 2015-05-06 2016-11-10 南开大学 Negative electrode material, preparation method therefor, and lithium-ion secondary battery using the negative electrode material
WO2017190364A1 (en) * 2016-05-06 2017-11-09 深圳先进技术研究院 Secondary battery and preparation method therefor
CN107240672A (en) * 2017-05-08 2017-10-10 禾畚兴业有限公司 A kind of method for adding graphene in the positive and negative pole plate of lithium battery
CN107611356A (en) * 2017-07-18 2018-01-19 深圳市沃特玛电池有限公司 A kind of silicon-carbon cathode lithium ion battery
CN108808073A (en) * 2018-06-29 2018-11-13 深圳鑫鹏能技术科技有限公司 A kind of silicon lithium tantalum capacitor batteries

Also Published As

Publication number Publication date
CN112490431A (en) 2021-03-12

Similar Documents

Publication Publication Date Title
WO2022126858A1 (en) Silicon-lithium battery and manufacturing method thereof
CN111987375A (en) Boehmite/inert lithium powder composite slurry, lithium-supplementing negative plate, preparation method of negative plate and lithium ion battery
CN110993358A (en) Flexible zinc ion capacitor
CN111326717B (en) Aluminum negative electrode material, preparation method and secondary battery
CN114552125B (en) Nondestructive lithium supplement composite diaphragm and preparation method and application thereof
CN108878893B (en) Modified current collector for negative electrode of quick-charging lithium ion battery and preparation method thereof
CN114551900B (en) Multifunctional current collector and preparation method and application thereof
CN113451576A (en) Graphite composite material, preparation method thereof and lithium ion battery
CN114709367B (en) Negative plate, lithium ion battery and preparation method of negative plate
CN113066962A (en) Silicon-containing negative plate and high-energy-density battery
CN116779870A (en) Negative electrode material for lithium metal battery, preparation method and application
Hu et al. Graphene film with folds for a stable lithium metal anode
CN116376280A (en) Poly (p-phenylene benzobisoxazole) porous membrane, preparation method and application thereof, composite membrane and battery
CN113809387B (en) Lithium iron phosphate lithium battery
CN115548262A (en) Negative pole piece, secondary battery and electric equipment
CN113594439A (en) Lithium supplement material, negative plate and battery
CN114759164A (en) Preparation method and application of lithium battery negative plate
CN114094076B (en) Negative plate and lithium ion battery comprising same
CN113964293B (en) Cyclic stable quick-charging type lithium ion battery cathode and application thereof
CN117878432B (en) Battery cell, and preparation method and application thereof
CN115172666B (en) Double-layer composite graphite negative electrode and preparation method thereof
CN113506909B (en) Lithium battery and electrolyte thereof
CN118738511A (en) Solid-state battery and consumer
CN116470018A (en) High-performance bimetal selenide/nitrogen-doped carbon composite material for negative electrode material of sodium ion battery
CN117117079A (en) Lithium battery negative plate and preparation method and application thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21904801

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 27/09/2023)

122 Ep: pct application non-entry in european phase

Ref document number: 21904801

Country of ref document: EP

Kind code of ref document: A1