WO2018133288A1 - Lithium battery current collector having protection function - Google Patents

Lithium battery current collector having protection function Download PDF

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Publication number
WO2018133288A1
WO2018133288A1 PCT/CN2017/087277 CN2017087277W WO2018133288A1 WO 2018133288 A1 WO2018133288 A1 WO 2018133288A1 CN 2017087277 W CN2017087277 W CN 2017087277W WO 2018133288 A1 WO2018133288 A1 WO 2018133288A1
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Prior art keywords
lithium battery
current collector
battery current
metal
conductive
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PCT/CN2017/087277
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French (fr)
Chinese (zh)
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杨铨铨
盛建民
刘浩涵
祝天舒
王军
闵国全
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上海长园维安电子线路保护有限公司
上海产业技术研究院
上海劲融投资管理有限公司
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Publication of WO2018133288A1 publication Critical patent/WO2018133288A1/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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/613—Cooling or keeping cold
    • 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
    • H01M4/64—Carriers or collectors
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/574—Devices or arrangements for the interruption of current
    • 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 present invention relates to a lithium battery current collector having a protective function, and more particularly to a lithium battery current collector in which a conductive composite material layer having a positive temperature effect of resistance is tightly bonded to both sides of a metal foil.
  • lithium is used for the current collector of the lithium battery and Cu for the negative electrode. Because aluminum will intercalate lithium at a low potential, it is not suitable for a negative current collector; copper will oxidize at a high potential, and it is not suitable for a positive current collector, but the aluminum surface has a passivation layer, so it can be used as a positive current collector.
  • the polymer-based conductive composite material can maintain a low resistance value under normal temperature, and has a characteristic of being sensitive to temperature changes, that is, when an overcurrent or an overheating phenomenon occurs in the circuit, the resistance thereof instantaneously increases to a high resistance value.
  • the circuit is in an open state to achieve the purpose of protecting circuit components. Therefore, the protective element prepared from the polymer-based conductive composite material can be connected to the circuit as a material of the current sensing element. Such materials have been widely used in electronic circuit protection components.
  • lithium batteries have been rapidly developed.
  • the energy density, power density, and cycle life of lithium batteries have increased significantly over the past two decades.
  • Reliable high-performance lithium-ion batteries are in strong demand in consumer electronics, electric vehicles, and grid energy storage.
  • the production capacity of the enterprises and battery capacity continues to increase. From the stage of the industry life cycle, the lithium battery industry is currently in a rapid growth period.
  • the safety of lithium batteries has not been completely solved.
  • the expansion of lithium-ion batteries in the application field makes the voltage and capacity of the battery system require more single cells to achieve, plus the package design, system design, BMS It is difficult to be perfect in management and other aspects.
  • the polymer PTC thermistor can be used to prevent the lithium battery from overheating.
  • the polymer PTC thermistor assembled outside the lithium battery is far away from the heat generating part of the battery, and the polymer PTC is thermally attenuated due to the decay of heat during the transfer.
  • the resistor cannot detect the abnormal rise of the internal temperature of the lithium battery in time, and it is difficult to protect the lithium battery in the first time.
  • the object of the invention is: a lithium battery current collector with a protection function, the lithium battery current collector with protection function is more effective in preventing thermal runaway of the lithium battery, and can quickly make an abnormal temperature and abnormal current inside the lithium battery Responsive and can be repeated multiple times.
  • the invention combines the polymer-based conductive composite material with the positive temperature effect of the resistor with the current lithium battery current collector, and forms a layered product inside the lithium battery, which is more effective in preventing thermal runaway of the lithium battery, the invention
  • the advantage is that it can respond quickly to abnormal temperatures and abnormal currents inside the lithium battery and can be repeatedly protected. It is a lithium battery current collector that tightly bonds a conductive composite material layer having a positive temperature effect on a metal foil. When the internal temperature of the lithium battery rises abnormally, the lithium battery can be protected at the first time.
  • the metal foil may be an aluminum foil and a copper foil having a thickness of between 1 ⁇ m and 30 ⁇ m.
  • the conductive composite material layer comprises at least one polymer substrate and at least one conductive powder having a resistivity of less than 200 ⁇ cm and a particle size distribution ranging from 0.01 ⁇ m to 50 ⁇ m, wherein:
  • the polymer substrate is: polyethylene, chlorinated polyethylene, oxidized polyethylene, polyvinyl chloride, butadiene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polystyrene, poly Carbonate, polyamide, polyimide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, polyphenylene sulfide, polyoxymethylene, phenolic resin, polytetrafluoroethylene , tetrafluoroethylene-hexafluoropropylene copolymer, polytrifluoroethylene, polyvinyl fluoride, maleic anhydride grafted polyethylene, polypropylene, polyvinylidene fluoride, epoxy resin, ethylene-vinyl acetate copolymer, polymethyl One of methyl acrylate, ethylene-acrylic acid copolymer, and mixtures thereof.
  • the conductive powder is selected from the group consisting of carbon-based conductive powders, metal powders, composite conductive powders, conductive ceramic powders, and mixtures thereof.
  • the carbon-based conductive powder is carbon black, carbon fiber, carbon nanotube, graphite, graphene, and a mixture thereof.
  • the metal powder is one of copper, nickel, cobalt, iron, tungsten, tin, lead, silver, gold, platinum or an alloy thereof and a mixture thereof.
  • the composite conductive powder is one of a carbon-based conductive material-coated metal powder and a carbon-based conductive material-coated conductive ceramic powder, and a mixture thereof.
  • the carbon-based conductive material is: carbon black, carbon fiber, carbon nanotube, graphite, graphene, and a mixture thereof.
  • the conductive ceramic powder is a mixture of one or more of a metal nitride, a metal carbide, a metal boride, a metal silicide, and a layered structure ceramic powder.
  • the metal boride is lanthanum boride, lanthanum diboride, vanadium boride, vanadium diboride, zirconium diboride, titanium diboride, lanthanum boride, lanthanum diboride, molybdenum boride, penta boron
  • molybdenum diboride, lanthanum diboride, diboron boride, tungsten boride, boron diboride, chromium boride, chromium diboride or chromium triboride is lanthanum boride, lanthanum diboride, vanadium boride, vanadium diboride, zirconium diboride, titanium diboride, lanthanum boride, lanthanum diboride, molybdenum boride, penta boron
  • the nitride is one of tantalum nitride, vanadium nitride, zirconium nitride, titanium nitride, tantalum nitride or tantalum nitride.
  • the carbide is one of tantalum carbide, vanadium carbide, zirconium carbide, titanium carbide, tantalum carbide, molybdenum carbide, tantalum carbide, tungsten carbide, tungsten carbide or trichromium.
  • the silicide is lanthanum silicide, lanthanum trisilicate, lanthanum silicide, vanadium disilicide, zirconium disilicide, titanium disilicide, bismuth silicate, bismuth disilicide, molybdenum disilicide, bismuth silicide, bismuth silicide One of silicon trioxide or chromium disilicate.
  • the invention provides a method for preparing a lithium battery current collector having a protection function, that is, the method for combining the conductive composite material layer and the metal foil sheet is thermal pressing, electrostatic spraying, plasma spraying, coating and printing. One or several of the thermal sprays.
  • the lithium battery current collector having the protective function has a thickness of between 5 ⁇ m and 50 ⁇ m, preferably 5 ⁇ m - 30 ⁇ m.
  • the lithium battery current collector with protection function provided by the invention has the advantages that the conductive composite material layer having the positive temperature effect of the resistance is tightly combined on the lithium battery current collector on both sides of the metal foil, when the lithium battery has an abnormal temperature inside,
  • the resistance of the conductive composite layer with positive resistance effect will increase sharply, cut off the circuit, which will be more effective in preventing thermal runaway of the lithium battery, and can respond quickly to abnormal temperature and abnormal current inside the lithium battery and can be more Repeated protection.
  • FIG. 1 is a schematic view showing the structure of a current collector of a lithium battery having a protection function according to the present invention
  • FIG. 2 is a schematic view showing the structure of a lithium battery prepared by using the lithium battery current collector having the protective function of the present invention.
  • the specific embodiment is as follows:
  • the polymer substrate is: polyethylene, chlorinated polyethylene, oxidized polyethylene, polyvinyl chloride, butadiene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polystyrene, polycarbonate , polyamide, polyimide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, polyphenylene sulfide, polyoxymethylene, phenolic resin, polytetrafluoroethylene, four Fluoroethylene-hexafluoropropylene copolymer, polytrifluoroethylene, polyvinyl fluoride, maleic anhydride grafted polyethylene, polypropylene, polyvinylidene fluoride, epoxy resin, ethylene-vinyl acetate copolymer, polymethyl methacrylate One of an ester, an ethylene-acrylic acid copolymer, and a mixture thereof;
  • the conductive powder has a resistivity of not more than 200 ⁇ cm and a particle diameter distribution ranging from 0.01 ⁇ m to 50 ⁇ m, and the conductive powder is selected from the group consisting of carbon-based conductive powders, metal powders, composite conductive powders, conductive ceramic powders, and mixtures thereof.
  • Polyethylene and conductive ceramic powder are compounded according to the ratio of PTC resistance.
  • the temperature of the internal mixer is set to 180 degrees and the rotation speed is 30 rpm.
  • the polymer is firstly mixed for 3 minutes, then the conductive filler is added to continue the density. After 15 minutes of smelting, the material was discharged to obtain a conductive composite material having a positive temperature effect of resistance.
  • melt-mixed conductive composite material having a positive electric resistance effect is calendered by an open mill to obtain a conductive composite material sheet having a positive temperature effect of 0.1 mm in thickness, which is then hot pressed to a thickness of 0.02 mm.
  • Conductive composite layer with positive temperature effect of resistance is calendered by an open mill to obtain a conductive composite material sheet having a positive temperature effect of 0.1 mm in thickness, which is then hot pressed to a thickness of 0.02 mm.
  • thermocompression temperature was 180 ° C
  • pressure was 12 MPa
  • time was 10 minutes
  • the ratio and processing procedure of the conductive composite material having the positive temperature effect of the resistance was the same as in the first embodiment except that the metal copper foil was changed to a metal aluminum foil.
  • Polyethylene and conductive ceramic powder are compounded according to the ratio of PTC resistance.
  • the temperature of the internal mixer is set to 180 degrees and the rotation speed is 30 rpm.
  • the polymer is firstly mixed for 3 minutes, then the conductive filler is added to continue the density. After 15 minutes of smelting, the conductive composite material having a positive temperature effect of resistance was obtained, which was then pulverized into granules.
  • the pulverized particles are subjected to multilayer co-extrusion to prepare a protective lithium battery current collector having a sandwich structure of a conductive composite material layer, a metal copper foil sheet and a conductive composite material layer, and have a total thickness of 0.05 mm.
  • the prepared lithium battery current collector with protection function can be assembled into a lithium battery, as shown in FIG.
  • the copper foil sheet 220 is tightly bonded to the first and second conductive composite material layers 210a and 210b having positive temperature effects on both sides, and is coated on the first and second conductive composite material layers 210a and 210b having positive temperature effects respectively.
  • the second negative electrode material layers 250a, 250b, the first and second positive electrode material layers 240a, 240b are coated on the aluminum foils 270b and 270a, respectively, and the second positive electrode material layer 240b and the first negative electrode material layer 250a are separated by a separator 260a.
  • the first positive electrode material layer 240a and the second negative electrode material layer 250b are separated by a separator 260b, between the second positive electrode material layer 240b and the separator 260a, and between the first negative electrode material layer 250a and the separator 260a. It is an electrolyte 230b; between the first positive electrode material layer 240a and the separator 260b, and between the second negative electrode material layer 250b and the separator 260b is an electrolyte 230a, and finally the entire component is sealed with an aluminum mold, and the positive electrode is electrically led out.
  • Aluminum foil and negative copper foil form a simple lithium battery.
  • the resistance of the first and second conductive composite layers 210a, 210b having the positive temperature effect of the resistor will increase sharply, and the path of the resistor is cut off to prevent thermal runaway of the lithium battery, and the lithium battery can be used.
  • the internal abnormal temperature and abnormal current make a quick response.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

Disclosed is a lithium battery current collector having a protection function, comprising: a metal foil, wherein the metal foil has a first surface and a second surface opposite to each other, and is used as a base foil of the lithium battery current collector; a first conductive composite layer having a positive temperature coefficient of resistance, the first conductive composite layer being closely bonded to the first surface of the metal foil; and a second conductive composite layer having the positive temperature coefficient of resistance, the second conductive composite layer being closely bonded to the second surface of the metal foil. The lithium battery current collector having a protection function can effectively avoid thermal runaway of lithium batteries and improve the safety performance of the lithium batteries.

Description

具有保护功能的锂电池集流体Lithium battery current collector with protection function 技术领域Technical field
本发明涉及一种具有保护功能的锂电池集流体，特别是一种将具有电阻正温度效应的导电复合材料层紧密结合在金属箔片两面的锂电池集流体。The present invention relates to a lithium battery current collector having a protective function, and more particularly to a lithium battery current collector in which a conductive composite material layer having a positive temperature effect of resistance is tightly bonded to both sides of a metal foil.
背景技术Background technique
一般情况下，锂电池的集流体正极用Al，负极用Cu。因为铝在低电位下会嵌锂，不宜做负极集流体；铜在高电位下会氧化，不宜做正极集流体，但铝表面有钝化层，因此可以作为正极集流体。In general, lithium is used for the current collector of the lithium battery and Cu for the negative electrode. Because aluminum will intercalate lithium at a low potential, it is not suitable for a negative current collector; copper will oxidize at a high potential, and it is not suitable for a positive current collector, but the aluminum surface has a passivation layer, so it can be used as a positive current collector.
高分子基导电复合材料在正常温度下可维持较低的电阻值，具有对温度变化反应敏锐的特性，即当电路中发生过电流或过高温现象时，其电阻会瞬间增加到一高阻值，使电路处于断路状态，以达到保护电路元件的目的。因此可把高分子基导电复合材料制备的保护元件连接到电路中，作为电流传感元件的材料。此类材料已被广泛应用于电子线路保护元器件上。The polymer-based conductive composite material can maintain a low resistance value under normal temperature, and has a characteristic of being sensitive to temperature changes, that is, when an overcurrent or an overheating phenomenon occurs in the circuit, the resistance thereof instantaneously increases to a high resistance value. The circuit is in an open state to achieve the purpose of protecting circuit components. Therefore, the protective element prepared from the polymer-based conductive composite material can be connected to the circuit as a material of the current sensing element. Such materials have been widely used in electronic circuit protection components.
近年来，锂电池得到迅速发展，锂电池的能量密度、功率密度、循环寿命在过去二十年有了显著提高，可靠的高性能锂离子电池在消费电子、电动汽车和电网能量储存领域需求强劲，从业企业、电池产能产量持续增加，从行业生命周期的阶段来看，锂电池行业目前处于快速成长期。但是锂电池的安全问题一直未完全解决，锂离子电池在应用领域的拓展，使得电池系统的电压和容量需要更多的单体电池来实现，加上pack成组时，系统的设计、BMS的管理等方面很难做到完美，一旦电池在滥用条件下(如过充、内或外部短路、高温等情况)，会出现热失控，进而引发起火、爆炸等安全事故，安全问题已经是高能量密度电池大规模应用的主要障碍。In recent years, lithium batteries have been rapidly developed. The energy density, power density, and cycle life of lithium batteries have increased significantly over the past two decades. Reliable high-performance lithium-ion batteries are in strong demand in consumer electronics, electric vehicles, and grid energy storage. The production capacity of the enterprises and battery capacity continues to increase. From the stage of the industry life cycle, the lithium battery industry is currently in a rapid growth period. However, the safety of lithium batteries has not been completely solved. The expansion of lithium-ion batteries in the application field makes the voltage and capacity of the battery system require more single cells to achieve, plus the package design, system design, BMS It is difficult to be perfect in management and other aspects. Once the battery is under abuse conditions (such as overcharge, internal or external short circuit, high temperature, etc.), there will be thermal runaway, which will lead to fire, explosion and other safety accidents. The safety problem is already high energy. The main obstacle to the large-scale application of density batteries.
为了提升电池的安全性能，人们已经进行了许多努力，包括隔膜和电解液稳定剂等。但是，这些方法都是不可逆的，因此一旦保护发生，电池无法再次使用。高分子PTC热敏电阻可以用来防止锂电池过热，但是，组装在锂电池外部的高分子PTC热敏电阻远离电池内部热量产生部位，由于热量在传递过程中的衰减，使得高分子PTC热敏电阻无法及时检测到锂电池内部温度的异常上升，难以在第一时间对锂电池进行保护。In order to improve the safety of the battery, many efforts have been made, including diaphragms and electrolyte stabilizers. However, these methods are irreversible, so once protection occurs, the battery cannot be used again. The polymer PTC thermistor can be used to prevent the lithium battery from overheating. However, the polymer PTC thermistor assembled outside the lithium battery is far away from the heat generating part of the battery, and the polymer PTC is thermally attenuated due to the decay of heat during the transfer. The resistor cannot detect the abnormal rise of the internal temperature of the lithium battery in time, and it is difficult to protect the lithium battery in the first time.
因此，为了更加及时有效地保护锂电池，必须开发出新的解决方案。Therefore, in order to protect lithium batteries more timely and effectively, new solutions must be developed.
发明内容 Summary of the invention
本发明目的在于：一种具有保护功能的锂电池集流体，该具有保护功能的锂电池集流体将在防止锂电池热失控上更有效，可以对锂电池内部的异常温度和异常电流做出快速响应且可以多次重复保护。The object of the invention is: a lithium battery current collector with a protection function, the lithium battery current collector with protection function is more effective in preventing thermal runaway of the lithium battery, and can quickly make an abnormal temperature and abnormal current inside the lithium battery Responsive and can be repeated multiple times.
本发明的目的通过下述技术方案实现：一种具有保护功能的锂电池集流体，包括金属箔片，其包含The object of the present invention is achieved by the following technical solution: a lithium battery current collector having a protective function, including a metal foil, which comprises
(a)所述的金属箔片,具有两个相对的第一表面和第二表面，作为锂电池集流体的基箔；(a) The metal foil sheet having two opposite first surfaces and a second surface as a base foil of a lithium battery current collector;
(b)具有电阻正温度效应的第一导电复合材料层，紧密结合在所述金属箔片的第一表面；(b) a first conductive composite layer having a positive temperature effect of resistance, tightly bonded to the first surface of the metal foil;
(c)具有电阻正温度效应的第二导电复合材料层，紧密结合在所述金属箔片的第二表面。(c) a second layer of electrically conductive composite having a positive temperature effect of electrical resistance, tightly bonded to the second surface of the metal foil.
本发明将具有电阻正温度效应的高分子基导电复合材料与现有锂电池集流体复合，构成一种层状产品置于锂电池内部，将在防止锂电池热失控上更有效，此发明的优点在于其可以对锂电池内部的异常温度和异常电流做出快速响应且可以多次重复保护。是一种将具有电阻正温度效应的导电复合材料层紧密结合在金属箔片两面的锂电池集流体。当锂电池内部温度异常上升时，可以在第一时间对锂电池进行保护。The invention combines the polymer-based conductive composite material with the positive temperature effect of the resistor with the current lithium battery current collector, and forms a layered product inside the lithium battery, which is more effective in preventing thermal runaway of the lithium battery, the invention The advantage is that it can respond quickly to abnormal temperatures and abnormal currents inside the lithium battery and can be repeatedly protected. It is a lithium battery current collector that tightly bonds a conductive composite material layer having a positive temperature effect on a metal foil. When the internal temperature of the lithium battery rises abnormally, the lithium battery can be protected at the first time.
所述金属箔片可以是铝箔和铜箔，其厚度介于为1μm～30μm之间。The metal foil may be an aluminum foil and a copper foil having a thickness of between 1 μm and 30 μm.
在上述方案基础上，所述导电复合材料层包含至少一种高分子基材和至少一种电阻率低于200μΩ.cm且粒径分布范围在0.01μm～50μm之间的导电粉末，其中：Based on the above solution, the conductive composite material layer comprises at least one polymer substrate and at least one conductive powder having a resistivity of less than 200 μΩ·cm and a particle size distribution ranging from 0.01 μm to 50 μm, wherein:
所述高分子基材为：聚乙烯、氯化聚乙烯、氧化聚乙烯、聚氯乙烯、丁二烯-丙烯腈共聚物、丙烯腈-丁二烯-苯乙烯共聚物、聚苯乙烯、聚碳酸酯、聚酰胺、聚酰亚胺、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚苯醚、聚苯硫醚、聚甲醛、酚醛树脂、聚四氟乙烯、四氟乙烯-六氟丙烯共聚物、聚三氟乙烯、聚氟乙烯、马来酸酐接枝聚乙烯、聚丙烯、聚偏氟乙烯、环氧树脂、乙烯-醋酸乙烯共聚物、聚甲基丙烯酸甲酯、乙烯-丙烯酸共聚物中的一种及其混合物。The polymer substrate is: polyethylene, chlorinated polyethylene, oxidized polyethylene, polyvinyl chloride, butadiene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polystyrene, poly Carbonate, polyamide, polyimide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, polyphenylene sulfide, polyoxymethylene, phenolic resin, polytetrafluoroethylene , tetrafluoroethylene-hexafluoropropylene copolymer, polytrifluoroethylene, polyvinyl fluoride, maleic anhydride grafted polyethylene, polypropylene, polyvinylidene fluoride, epoxy resin, ethylene-vinyl acetate copolymer, polymethyl One of methyl acrylate, ethylene-acrylic acid copolymer, and mixtures thereof.
所述导电粉末选自:碳系导电粉末、金属粉末、复合导电粉末、导电陶瓷粉末及它们的混合物。 The conductive powder is selected from the group consisting of carbon-based conductive powders, metal powders, composite conductive powders, conductive ceramic powders, and mixtures thereof.
所述碳系导电粉末为：碳黑、碳纤维、碳纳米管、石墨、石墨烯及它们的混合物。The carbon-based conductive powder is carbon black, carbon fiber, carbon nanotube, graphite, graphene, and a mixture thereof.
所述金属粉末为：铜、镍、钴、铁、钨、锡、铅、银、金、铂或其合金中的一种及其混合物。The metal powder is one of copper, nickel, cobalt, iron, tungsten, tin, lead, silver, gold, platinum or an alloy thereof and a mixture thereof.
所述复合导电粉末为：碳系导电材料包覆金属粉末和碳系导电材料包覆导电陶瓷粉末中的一种及其混合物。The composite conductive powder is one of a carbon-based conductive material-coated metal powder and a carbon-based conductive material-coated conductive ceramic powder, and a mixture thereof.
所述碳系导电材料为：碳黑、碳纤维、碳纳米管、石墨、石墨烯及它们的混合物。The carbon-based conductive material is: carbon black, carbon fiber, carbon nanotube, graphite, graphene, and a mixture thereof.
所述导电陶瓷粉末为：金属氮化物、金属碳化物、金属硼化物、金属硅化物、层状结构陶瓷粉之中的一种或几种的混合物。The conductive ceramic powder is a mixture of one or more of a metal nitride, a metal carbide, a metal boride, a metal silicide, and a layered structure ceramic powder.
所述金属硼化物为硼化钽、二硼化钽、硼化钒、二硼化钒、二硼化锆、二硼化钛、硼化铌、二硼化铌、硼化二钼、五硼化二钼、二硼化铪、硼化二钨、硼化钨、硼化二铬、硼化铬、二硼化铬或三硼化五铬之中的一种。所述氮化物为氮化钽、氮化钒、氮化锆、氮化钛、氮化铌或氮化铪中的一种。所述碳化物为碳化钽、碳化钒、碳化锆、碳化钛、碳化铌、碳化二钼、碳化铪、碳化钨、碳化二钨或二碳化三铬之中的一种。所述硅化物为二硅化钽、三硅化五钽、硅化三钒、二硅化钒、二硅化锆、二硅化钛、三硅化五钛、二硅化铌、二硅化钼、二硅化铪、二硅化钨、硅化三铬或二硅化铬之中的一种。所述层状结构陶瓷粉为Sc2InC、Ti2AlC、Ti2GaC、Ti2InC、Ti2TlC、V2AlC、V2GaC、Cr2GaC、Ti2AlN、Ti2GaN、Ti2InN、V2GaN、Cr2GaN、Ti2GeC、Ti2SnC、Ti2PbC、V2GeC、Cr2SiC、Cr2GeC、V2PC、V2AsC、Ti2SC、Zr2InC、Zr2TlC、Nb2AlC、Nb2GaC、Nb2InC、Mo2GaC、Zr2InN、Zr2TlN、Zr2SnC、Zr2PbC、Nb2SnC、Nb2PC、Nb2AsC、Zr2SC、Nb2SC、Hf2SC、Hf2InC、Hf2TlC、Ta2AlC、Ta2GaC、Hf2SnC、Hf2PbC、Hf2SnN、Ti3AlC2、V3AlC2、Ta3AlC2、Ti3SiC2、Ti3GeC2、Ti3SnC2、Ti4AlN3、V4AlC3、Ti4GaC3、Nb4AlN3、Ta4AlC3、Ti4SiC3、Ti4GeC3之中的一种及其混合物。The metal boride is lanthanum boride, lanthanum diboride, vanadium boride, vanadium diboride, zirconium diboride, titanium diboride, lanthanum boride, lanthanum diboride, molybdenum boride, penta boron One of molybdenum diboride, lanthanum diboride, diboron boride, tungsten boride, boron diboride, chromium boride, chromium diboride or chromium triboride. The nitride is one of tantalum nitride, vanadium nitride, zirconium nitride, titanium nitride, tantalum nitride or tantalum nitride. The carbide is one of tantalum carbide, vanadium carbide, zirconium carbide, titanium carbide, tantalum carbide, molybdenum carbide, tantalum carbide, tungsten carbide, tungsten carbide or trichromium. The silicide is lanthanum silicide, lanthanum trisilicate, lanthanum silicide, vanadium disilicide, zirconium disilicide, titanium disilicide, bismuth silicate, bismuth disilicide, molybdenum disilicide, bismuth silicide, bismuth silicide One of silicon trioxide or chromium disilicate. The layered structure of ceramic powder Sc 2 InC, Ti 2 AlC, Ti 2 GaC, Ti 2 InC, Ti 2 TlC, V 2 AlC, V 2 GaC, Cr 2 GaC, Ti 2 AlN, Ti 2 GaN, Ti 2 InN, V 2 GaN, Cr 2 GaN, Ti 2 GeC, Ti 2 SnC, Ti 2 PbC, V 2 GeC, Cr 2 SiC, Cr 2 GeC, V 2 PC, V 2 AsC, Ti 2 SC, Zr 2 InC, Zr 2 TlC, Nb 2 AlC, Nb 2 GaC, Nb 2 InC, Mo 2 GaC, Zr 2 InN, Zr 2 TlN, Zr 2 SnC, Zr 2 PbC, Nb 2 SnC, Nb 2 PC, Nb 2 AsC, Zr 2 SC, Nb 2 SC, Hf 2 SC, Hf 2 InC, Hf 2 TlC, Ta 2 AlC, Ta 2 GaC, Hf 2 SnC, Hf 2 PbC, Hf 2 SnN, Ti 3 AlC 2 , V 3 AlC 2 , Ta 3 AlC 2 , Ti 3 SiC 2 , Ti 3 GeC 2 , Ti 3 SnC 2 , Ti 4 AlN 3 , V 4 AlC 3 , Ti 4 GaC 3 , Nb 4 AlN 3 , Ta 4 AlC 3 , Ti 4 SiC 3 , Ti 4 One of GeC 3 and a mixture thereof.
本发明提供一种具有保护功能的锂电池集流体的制法，即：所述导电复合材料层与所述金属箔片结合的方法是热压合、静电喷涂、等离子体喷涂、涂布、印刷、热喷涂之中的一种或几种。The invention provides a method for preparing a lithium battery current collector having a protection function, that is, the method for combining the conductive composite material layer and the metal foil sheet is thermal pressing, electrostatic spraying, plasma spraying, coating and printing. One or several of the thermal sprays.
所述具有保护功能的锂电池集流体的厚度介于5μm-50μm之间，优选为 5μm-30μm。The lithium battery current collector having the protective function has a thickness of between 5 μm and 50 μm, preferably 5 μm - 30 μm.
本发明提供的具有保护功能的锂电池集流体，优越性在于：将具有电阻正温度效应的导电复合材料层紧密结合在金属箔片两面的锂电池集流体，当锂电池内部有异常温度时，具有电阻正稳定效应的导电复合材料层的电阻将会剧增，截断电路，这将在防止锂电池热失控上更有效，可以对锂电池内部的异常温度和异常电流做出快速响应且可以多次重复保护。The lithium battery current collector with protection function provided by the invention has the advantages that the conductive composite material layer having the positive temperature effect of the resistance is tightly combined on the lithium battery current collector on both sides of the metal foil, when the lithium battery has an abnormal temperature inside, The resistance of the conductive composite layer with positive resistance effect will increase sharply, cut off the circuit, which will be more effective in preventing thermal runaway of the lithium battery, and can respond quickly to abnormal temperature and abnormal current inside the lithium battery and can be more Repeated protection.
附图说明DRAWINGS
图1本发明的具有保护功能的锂电池集流体结构示意图；1 is a schematic view showing the structure of a current collector of a lithium battery having a protection function according to the present invention;
图2利用本发明的具有保护功能的锂电池集流体制备的锂电池结构示意图。2 is a schematic view showing the structure of a lithium battery prepared by using the lithium battery current collector having the protective function of the present invention.
具体实施方式detailed description
对于本发明的具有保护功能的锂电池集流体，其具体实施方式如下：For the lithium battery current collector having the protective function of the present invention, the specific embodiment is as follows:
具有电阻正温度效应的导电复合材料中，In a conductive composite material having a positive temperature effect of resistance,
高分子基材为：聚乙烯、氯化聚乙烯、氧化聚乙烯、聚氯乙烯、丁二烯-丙烯腈共聚物、丙烯腈-丁二烯-苯乙烯共聚物、聚苯乙烯、聚碳酸酯、聚酰胺、聚酰亚胺、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚苯醚、聚苯硫醚、聚甲醛、酚醛树脂、聚四氟乙烯、四氟乙烯-六氟丙烯共聚物、聚三氟乙烯、聚氟乙烯、马来酸酐接枝聚乙烯、聚丙烯、聚偏氟乙烯、环氧树脂、乙烯-醋酸乙烯共聚物、聚甲基丙烯酸甲酯、乙烯-丙烯酸共聚物中的一种及其混合物；The polymer substrate is: polyethylene, chlorinated polyethylene, oxidized polyethylene, polyvinyl chloride, butadiene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polystyrene, polycarbonate , polyamide, polyimide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, polyphenylene sulfide, polyoxymethylene, phenolic resin, polytetrafluoroethylene, four Fluoroethylene-hexafluoropropylene copolymer, polytrifluoroethylene, polyvinyl fluoride, maleic anhydride grafted polyethylene, polypropylene, polyvinylidene fluoride, epoxy resin, ethylene-vinyl acetate copolymer, polymethyl methacrylate One of an ester, an ethylene-acrylic acid copolymer, and a mixture thereof;
导电粉末的电阻率不大于200μΩ.cm且粒径分布范围在0.01μm～50μm之间，所述导电粉末选自:碳系导电粉末、金属粉末、复合导电粉末、导电陶瓷粉末及它们的混合物。The conductive powder has a resistivity of not more than 200 μΩ·cm and a particle diameter distribution ranging from 0.01 μm to 50 μm, and the conductive powder is selected from the group consisting of carbon-based conductive powders, metal powders, composite conductive powders, conductive ceramic powders, and mixtures thereof.
实施例1Example 1
将聚乙烯、导电陶瓷粉末按PTC电阻的配比配料，将密炼机温度设定为180度，转速为30转/分钟，先加入聚合物密炼3分钟后，然后加入导电填料，继续密炼15分钟后出料，得到具有电阻正温度效应的导电复合材料。Polyethylene and conductive ceramic powder are compounded according to the ratio of PTC resistance. The temperature of the internal mixer is set to 180 degrees and the rotation speed is 30 rpm. The polymer is firstly mixed for 3 minutes, then the conductive filler is added to continue the density. After 15 minutes of smelting, the material was discharged to obtain a conductive composite material having a positive temperature effect of resistance.
将上述熔融混合好的具有电阻正温度效应的导电复合材料通过开炼机压延，得到厚度为0.1毫米的具有电阻正温度效应的导电复合材料片材，再将其热压成0.02毫米厚的具有电阻正温度效应的导电复合材料层。 The above-mentioned melt-mixed conductive composite material having a positive electric resistance effect is calendered by an open mill to obtain a conductive composite material sheet having a positive temperature effect of 0.1 mm in thickness, which is then hot pressed to a thickness of 0.02 mm. Conductive composite layer with positive temperature effect of resistance.
将两片具有电阻正温度效应的第一、第二导电复合材料层110a、110b，按图1所示置于金属铜箔片120两面。通过热压合的方法将上述三层叠好紧密结合在一起。热压合的温度为180摄氏度，压力为12兆帕，时间为10分钟，最后在冷压机上冷压10分钟，得到图1所示的具有保护功能的锂电池集流体。Two sheets of the first and second conductive composite layers 110a, 110b having positive resistance effects of temperature are placed on both sides of the metal copper foil 120 as shown in FIG. The above three layers are tightly bonded together by a thermocompression bonding method. The thermocompression temperature was 180 ° C, the pressure was 12 MPa, the time was 10 minutes, and finally cold pressed on a cold press for 10 minutes to obtain a lithium battery current collector having a protective function as shown in FIG.
实施例2Example 2
具有电阻正温度效应的导电复合材料配比和加工工艺与实施例1相同，只是将金属铜箔改为金属铝箔。The ratio and processing procedure of the conductive composite material having the positive temperature effect of the resistance was the same as in the first embodiment except that the metal copper foil was changed to a metal aluminum foil.
应用例1Application example 1
将聚乙烯、导电陶瓷粉末按PTC电阻的配比配料，将密炼机温度设定为180度，转速为30转/分钟，先加入聚合物密炼3分钟后，然后加入导电填料，继续密炼15分钟后出料，得到具有电阻正温度效应的导电复合材料，然后将其粉碎成颗粒。Polyethylene and conductive ceramic powder are compounded according to the ratio of PTC resistance. The temperature of the internal mixer is set to 180 degrees and the rotation speed is 30 rpm. The polymer is firstly mixed for 3 minutes, then the conductive filler is added to continue the density. After 15 minutes of smelting, the conductive composite material having a positive temperature effect of resistance was obtained, which was then pulverized into granules.
将上述粉碎的颗粒经过多层共挤，制备成导电复合材料层、金属铜箔片和导电复合材料层的三明治结构的具有保护功能的锂电池集流体，总厚度为0.05毫米。The pulverized particles are subjected to multilayer co-extrusion to prepare a protective lithium battery current collector having a sandwich structure of a conductive composite material layer, a metal copper foil sheet and a conductive composite material layer, and have a total thickness of 0.05 mm.
制备的具有保护功能的锂电池集流体可以装配到锂电池中，如图2所示。铜箔片220两面紧密结合具有正温度效应的第一、第二导电复合材料层210a和210b，在具有正温度效应的第一、第二导电复合材料层210a、210b上分别涂布第一、第二负极材料层250a、250b,第一、第二正极材料层240a、240b分别涂布在铝箔270b和270a上，第二正极材料层240b与第一负极材料层250a之间用隔膜一260a隔开；第一正极材料层240a与第二负极材料层250b之间用隔膜二260b隔开,第二正极材料层240b与隔膜一260a之间，以及第一负极材料层250a与隔膜一260a之间为电解液230b；第一正极材料层240a与隔膜二260b之间，以及第二负极材料层250b与隔膜二260b之间为电解液230a,最后将整个部件用铝塑模密封包裹，电气引出正极铝箔和负极铜箔，即形成一个简单的锂电池。当锂电池内部有异常温度时，具有电阻正温度效应的第一、第二导电复合材料层210a、210b的电阻将会剧增，截断电阻的通路，防止锂电池热失控发生，可以对锂电池内部的异常温度和异常电流做出快速响应。The prepared lithium battery current collector with protection function can be assembled into a lithium battery, as shown in FIG. The copper foil sheet 220 is tightly bonded to the first and second conductive composite material layers 210a and 210b having positive temperature effects on both sides, and is coated on the first and second conductive composite material layers 210a and 210b having positive temperature effects respectively. The second negative electrode material layers 250a, 250b, the first and second positive electrode material layers 240a, 240b are coated on the aluminum foils 270b and 270a, respectively, and the second positive electrode material layer 240b and the first negative electrode material layer 250a are separated by a separator 260a. The first positive electrode material layer 240a and the second negative electrode material layer 250b are separated by a separator 260b, between the second positive electrode material layer 240b and the separator 260a, and between the first negative electrode material layer 250a and the separator 260a. It is an electrolyte 230b; between the first positive electrode material layer 240a and the separator 260b, and between the second negative electrode material layer 250b and the separator 260b is an electrolyte 230a, and finally the entire component is sealed with an aluminum mold, and the positive electrode is electrically led out. Aluminum foil and negative copper foil form a simple lithium battery. When there is an abnormal temperature inside the lithium battery, the resistance of the first and second conductive composite layers 210a, 210b having the positive temperature effect of the resistor will increase sharply, and the path of the resistor is cut off to prevent thermal runaway of the lithium battery, and the lithium battery can be used. The internal abnormal temperature and abnormal current make a quick response.
本发明的内容和特点已揭示如上，然而前面叙述的本发明仅仅简要地或只 涉及本发明的特定部分，本发明的特征可能比在此公开的内容涉及的更多。因此，本发明的保护范围应不限于实施例所揭示的内容，而应该包括在不同部分中所体现的所有内容的组合，以及各种不背离本发明的替换和修饰，并为本发明的权利要求书所涵盖。 The content and features of the present invention have been disclosed above, however, the foregoing description of the present invention is only brief or only Features relating to the present invention may be more numerous than those disclosed herein. Therefore, the scope of the present invention should not be limited by the scope of the embodiments, but should include all combinations of the various elements in the various parts and the various alternatives and modifications without departing from the invention, and Covered in the request.

Claims (11)

  1. 一种具有保护功能的锂电池集流体，包括金属箔片，其特征在于：其包含A lithium battery current collector having a protection function, comprising a metal foil, characterized in that it comprises
    (a)所述的金属箔片,具有两个相对的第一表面和第二表面，作为锂电池集流体的基箔；(a) The metal foil sheet having two opposite first surfaces and a second surface as a base foil of a lithium battery current collector;
    (b)具有电阻正温度效应的第一导电复合材料层，紧密结合在所述金属箔片的第一表面；(b) a first conductive composite layer having a positive temperature effect of resistance, tightly bonded to the first surface of the metal foil;
    (c)具有电阻正温度效应的第二导电复合材料层，紧密结合在所述金属箔片的第二表面。(c) a second layer of electrically conductive composite having a positive temperature effect of electrical resistance, tightly bonded to the second surface of the metal foil.
  2. 根据权利要求1所述的具有保护功能的锂电池集流体，其特征在于所述金属箔片的厚度介于1μm～30μm之间。A lithium battery current collector having a protective function according to claim 1, wherein said metal foil has a thickness of between 1 μm and 30 μm.
  3. 根据权利要求1所述的具有保护功能的锂电池集流体，其特征在于所述导电复合材料层包含至少一种高分子基材和至少一种电阻率不大于200μΩ.cm且粒径分布范围在0.01μm～50μm之间的导电粉末，其中，所述高分子基材为：聚乙烯、氯化聚乙烯、氧化聚乙烯、聚氯乙烯、丁二烯-丙烯腈共聚物、丙烯腈-丁二烯-苯乙烯共聚物、聚苯乙烯、聚碳酸酯、聚酰胺、聚酰亚胺、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚苯醚、聚苯硫醚、聚甲醛、酚醛树脂、聚四氟乙烯、四氟乙烯-六氟丙烯共聚物、聚三氟乙烯、聚氟乙烯、马来酸酐接枝聚乙烯、聚丙烯、聚偏氟乙烯、环氧树脂、乙烯-醋酸乙烯共聚物、聚甲基丙烯酸甲酯、乙烯-丙烯酸共聚物中的一种及其混合物；所述导电粉末选自:碳系导电粉末、金属粉末、复合导电粉末、导电陶瓷粉末及它们的混合物。The lithium battery current collector according to claim 1, wherein the conductive composite material layer comprises at least one polymer substrate and at least one resistivity of not more than 200 μΩ·cm and a particle size distribution range of a conductive powder of between 0.01 μm and 50 μm, wherein the polymer substrate is: polyethylene, chlorinated polyethylene, oxidized polyethylene, polyvinyl chloride, butadiene-acrylonitrile copolymer, acrylonitrile-butyl Alkene-styrene copolymer, polystyrene, polycarbonate, polyamide, polyimide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, polyphenylene sulfide Ether, polyoxymethylene, phenolic resin, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, polytrifluoroethylene, polyvinyl fluoride, maleic anhydride grafted polyethylene, polypropylene, polyvinylidene fluoride, epoxy a resin, an ethylene-vinyl acetate copolymer, a polymethyl methacrylate, an ethylene-acrylic acid copolymer, and a mixture thereof; the conductive powder is selected from the group consisting of: a carbon-based conductive powder, a metal powder, a composite conductive powder, and a conductive ceramic Powders and mixtures thereof.
  4. 根据权利要求3所述的具有保护功能的锂电池集流体，其特征在于所述碳系导电粉末为：碳黑、碳纤维、碳纳米管、石墨、石墨烯及它们的混合物。The lithium battery current collector having a protective function according to claim 3, wherein the carbon-based conductive powder is carbon black, carbon fiber, carbon nanotube, graphite, graphene, and a mixture thereof.
  5. 根据权利要求3所述的具有保护功能的锂电池集流体，其特征在于所述金属粉末为：铜、镍、钴、铁、钨、锡、铅、银、金、铂或其合金中的一种及其混合物。The lithium battery current collector according to claim 3, wherein the metal powder is one of copper, nickel, cobalt, iron, tungsten, tin, lead, silver, gold, platinum or an alloy thereof. And their mixtures.
  6. 根据权利要求3所述的具有保护功能的锂电池集流体，其特征在于所述复合导电粉末为：碳系导电材料包覆金属粉末和碳系导电材料包覆导电陶瓷粉末中的一种及其混合物。 The lithium battery current collector having a protective function according to claim 3, wherein the composite conductive powder is one of a carbon-based conductive material-coated metal powder and a carbon-based conductive material-coated conductive ceramic powder mixture.
  7. 根据权利要求6所述的具有保护功能的锂电池集流体，其特征在于所述碳系导电材料为：碳黑、碳纤维、碳纳米管、石墨、石墨烯及它们的混合物。The lithium battery current collector having a protective function according to claim 6, wherein the carbon-based conductive material is carbon black, carbon fiber, carbon nanotube, graphite, graphene, and a mixture thereof.
  8. 根据权利要求3所述的具有保护功能的锂电池集流体，其特征在于所述导电陶瓷粉末为：金属氮化物、金属碳化物、金属硼化物、金属硅化物、层状结构陶瓷粉之中的一种或几种的混合物。The lithium battery current collector with protection function according to claim 3, wherein the conductive ceramic powder is: metal nitride, metal carbide, metal boride, metal silicide, layered structure ceramic powder a mixture of one or several.
  9. 根据权利要求8所述的具有保护功能的锂电池集流体，其特征在于，A lithium battery current collector having a protection function according to claim 8, wherein
    所述金属硼化物为硼化钽、二硼化钽、硼化钒、二硼化钒、二硼化锆、二硼化钛、硼化铌、二硼化铌、硼化二钼、五硼化二钼、二硼化铪、硼化二钨、硼化钨、硼化二铬、硼化铬、二硼化铬或三硼化五铬之中的一种；The metal boride is lanthanum boride, lanthanum diboride, vanadium boride, vanadium diboride, zirconium diboride, titanium diboride, lanthanum boride, lanthanum diboride, molybdenum boride, penta boron One of molybdenum diboride, lanthanum diboride, diboron boride, tungsten boride, boron diboride, chromium boride, chromium diboride or chromium triboride;
    所述金属氮化物为氮化钽、氮化钒、氮化锆、氮化钛、氮化铌或氮化铪中的一种；The metal nitride is one of tantalum nitride, vanadium nitride, zirconium nitride, titanium nitride, tantalum nitride or tantalum nitride;
    所述碳化物为碳化钽、碳化钒、碳化锆、碳化钛、碳化铌、碳化二钼、碳化铪、碳化钨、碳化二钨或二碳化三铬之中的一种；The carbide is one of tantalum carbide, vanadium carbide, zirconium carbide, titanium carbide, tantalum carbide, molybdenum carbide, tantalum carbide, tungsten carbide, tungsten carbide or trichromium;
    所述硅化物为二硅化钽、三硅化五钽、硅化三钒、二硅化钒、二硅化锆、二硅化钛、三硅化五钛、二硅化铌、二硅化钼、二硅化铪、二硅化钨、硅化三铬或二硅化铬之中的一种；The silicide is lanthanum silicide, lanthanum trisilicate, lanthanum silicide, vanadium disilicide, zirconium disilicide, titanium disilicide, bismuth silicate, bismuth disilicide, molybdenum disilicide, bismuth silicide, bismuth silicide One of silicon trisulphide or chromium disilicide;
    所述层状结构陶瓷粉为Sc2InC、Ti2AlC、Ti2GaC、Ti2InC、Ti2TlC、V2AlC、V2GaC、Cr2GaC、Ti2AlN、Ti2GaN、Ti2InN、V2GaN、Cr2GaN、Ti2GeC、Ti2SnC、Ti2PbC、V2GeC、Cr2SiC、Cr2GeC、V2PC、V2AsC、Ti2SC、Zr2InC、Zr2TlC、Nb2AlC、Nb2GaC、Nb2InC、Mo2GaC、Zr2InN、Zr2TlN、Zr2SnC、Zr2PbC、Nb2SnC、Nb2PC、Nb2AsC、Zr2SC、Nb2SC、Hf2SC、Hf2InC、Hf2TlC、Ta2AlC、Ta2GaC、Hf2SnC、Hf2PbC、Hf2SnN、Ti3AlC2、V3AlC2、Ta3AlC2、Ti3SiC2、Ti3GeC2、Ti3SnC2、Ti4AlN3、V4AlC3、Ti4GaC3、Nb4AlN3、Ta4AlC3、Ti4SiC3、Ti4GeC3之中的一种及其混合物。The layered structure of ceramic powder Sc 2 InC, Ti 2 AlC, Ti 2 GaC, Ti 2 InC, Ti 2 TlC, V 2 AlC, V 2 GaC, Cr 2 GaC, Ti 2 AlN, Ti 2 GaN, Ti 2 InN, V 2 GaN, Cr 2 GaN, Ti 2 GeC, Ti 2 SnC, Ti 2 PbC, V 2 GeC, Cr 2 SiC, Cr 2 GeC, V 2 PC, V 2 AsC, Ti 2 SC, Zr 2 InC, Zr 2 TlC, Nb 2 AlC, Nb 2 GaC, Nb 2 InC, Mo 2 GaC, Zr 2 InN, Zr 2 TlN, Zr 2 SnC, Zr 2 PbC, Nb 2 SnC, Nb 2 PC, Nb 2 AsC, Zr 2 SC, Nb 2 SC, Hf 2 SC, Hf 2 InC, Hf 2 TlC, Ta 2 AlC, Ta 2 GaC, Hf 2 SnC, Hf 2 PbC, Hf 2 SnN, Ti 3 AlC 2 , V 3 AlC 2 , Ta 3 AlC 2 , Ti 3 SiC 2 , Ti 3 GeC 2 , Ti 3 SnC 2 , Ti 4 AlN 3 , V 4 AlC 3 , Ti 4 GaC 3 , Nb 4 AlN 3 , Ta 4 AlC 3 , Ti 4 SiC 3 , Ti 4 One of GeC 3 and a mixture thereof.
  10. 根据权利要求1所述的具有保护功能的锂电池集流体，其特征在于，所述导电复合材料层与所述金属箔片结合的方法是热压合、静电喷涂、等离子体喷涂、涂布、印刷、热喷涂之中的一种或几种。The lithium battery current collector with protection function according to claim 1, wherein the conductive composite material layer and the metal foil are combined by thermocompression bonding, electrostatic spraying, plasma spraying, coating, One or several of printing and thermal spraying.
  11. 根据权利要求1或2所述的具有保护功能的锂电池集流体，其特征在于，所述具有保护功能的锂电池集流体的厚度介于5μm-50μm之间。 The lithium battery current collector having a protective function according to claim 1 or 2, wherein the lithium battery current collector having a protective function has a thickness of between 5 μm and 50 μm.
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