WO2017092572A1 - 锂离子电池隔膜及其制备方法 - Google Patents

锂离子电池隔膜及其制备方法 Download PDF

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WO2017092572A1
WO2017092572A1 PCT/CN2016/106247 CN2016106247W WO2017092572A1 WO 2017092572 A1 WO2017092572 A1 WO 2017092572A1 CN 2016106247 W CN2016106247 W CN 2016106247W WO 2017092572 A1 WO2017092572 A1 WO 2017092572A1
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lithium ion
ion battery
halloysite
battery separator
halloysite nanotube
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English (en)
French (fr)
Inventor
刘榛
尚玉明
何向明
王莉
李建军
王要武
高剑
赵鹏
钱冠男
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Tsinghua University
Jiangsu Huadong Institute of Li-ion Battery Co Ltd
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Tsinghua University
Jiangsu Huadong Institute of Li-ion Battery Co Ltd
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Publication of WO2017092572A1 publication Critical patent/WO2017092572A1/zh
Priority to US15/992,173 priority Critical patent/US20180277811A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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 the field of battery technology, and more particularly to a battery separator and a method of preparing the same.
  • Lithium-ion batteries have advantages such as high voltage, high energy density, long cycle life and no memory effect, making them widely used in notebook computers, mobile phones, and other portable electronic devices. At the same time, they have broad applications in aerospace technology and defense industry. The outlook has become a hot topic of current research.
  • the key components of lithium-ion batteries are mainly composed of positive electrode, negative electrode, diaphragm and electrolyte.
  • the separator is the core component of the lithium ion battery, and its performance has an important impact on the safety performance and electrochemical performance of the battery.
  • polyolefin microporous membranes such as polypropylene (PP) membranes, polyethylene (PE) membranes or multilayer composite membranes of both are used.
  • PP polypropylene
  • PE polyethylene
  • multilayer composite membranes of both are used.
  • high temperature resistant inorganic nanoparticles may be coated on the surface of the separator to enhance the thermal dimensional stability and wettability of the battery separator.
  • Commonly used inorganic nanoparticles are Al 2 O 3 , SiO 2 and TiO 2 , etc., but the wide application of the nano particles due to their high production cost, uneven dispersion, and easy water absorption.
  • a lithium ion battery separator comprising a diaphragm substrate and two halloysite nanotube coatings having opposite surfaces, the two halloysite nanotube coatings respectively disposed on the separator The two surfaces of the substrate are oppositely disposed.
  • the separator substrate is a porous structure having a plurality of micropores.
  • the two halloysite nanotube coatings are applied to the surface of the separator substrate.
  • the membrane substrate is a polyolefin microporous membrane.
  • the halloysite nanotube coating comprises an halloysite nanotube and a polymeric binder, the homologous nanotubes being uniformly mixed with the polymeric binder to form the halloysite nanotubes together Non-woven coating.
  • the polymer binder is one or both of polyurethane, polyvinylidene fluoride or polyimide.
  • a method for preparing a lithium ion battery separator comprising the steps of:
  • the halloysite nanotube raw material is a silane coupling agent-modified halloysite nanotube.
  • the solvent is one or both of tetrahydrofuran, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone.
  • the polymer binder is one of polyurethane, polyvinylidene fluoride or polyimide.
  • the invention uses a silane coupling agent to surface-modify the halloysite nanotubes, and uses a solution blending method to mix the binder polymer to prepare a membrane coating slurry for ceramification modification of the lithium battery separator. Thereby improving the thermal stability and corresponding electrochemical performance of the lithium ion battery.
  • the halloysite nanotubes have a unique tubular structure with a tube length of 1 to 15 microns and a diameter of 10 to 50 nanometers, which can be combined with a polymer to prepare an excellent polymer/inorganic nanocomposite.
  • FIG. 1 is a schematic structural view of a lithium ion battery separator according to an embodiment of the present invention.
  • FIG. 2 is a schematic enlarged view of the halloysite nanotube coating in the lithium ion battery separator of FIG. 1.
  • FIG. 3 is a scanning electron micrograph of a surface-modified halloysite nanotube material in a lithium ion battery separator according to an embodiment of the present invention.
  • FIG. 4 is a scanning electron micrograph of a halloysite nanotube coating composed of the halloysite nanotube material of FIG.
  • FIG. 5 is a flow chart of a method for preparing a separator for a lithium ion battery according to an embodiment of the present invention.
  • an embodiment of the present invention provides a separator 10 for a lithium ion battery, which includes a separator substrate 110 and two halloysite nanotube coatings 120 .
  • the diaphragm substrate 110 is a planar structure and is a film having a certain thickness.
  • the membrane substrate 110 has two opposing surfaces, and the two halloysite nanotube coatings 120 are disposed on opposite surfaces of the membrane substrate 110, respectively.
  • the separator substrate 110 is a polyolefin microporous film such as a polypropylene (PP) film, a polyethylene (PE) film, or a multilayer composite film of both.
  • the membrane substrate 110 has a plurality of micropores, and the two halloysite nanotube coatings 120 cover the surface of the porous membrane.
  • the separator substrate 110 is a polyethylene (PE) film having a thickness of 25 ⁇ m.
  • the halloysite nanotube coating 120 includes a plurality of halloysite nanotubes 122, and a polymer binder 124, and the plurality of halloysite nanotubes 122 are bonded to the polymer.
  • the agents 124 are combined to form the halloysite nanotube coating 120.
  • the polymeric binder 124 is one or both of polyurethane, polyvinylidene fluoride or polyimide. In this embodiment, the polymer binder 124 is polyimide.
  • the halloysite nanotubes 122 may be functionalized halloysite nanotubes, and the halloysite nanotubes may be surface-modified with a silane coupling agent through a covalent bond. Grafted to the surface of the halloysite nanotube 122. After the surface modification of the halloysite nanotubes 122, the polymeric binder 124 is uniformly dispersed in the halloysite nanotube coating 120. Further, referring to FIG. 4, the halloysite nanotubes 122 may be uniformly dispersed on two opposite surfaces of the separator substrate 110. It can be understood that the functionalization treatment of the halloysite nanotubes 122 is not limited to surface modification, and the functionalized treatment methods in the prior art that facilitate the dispersion of the halloysite nanotubes 122 are all applicable to the present invention.
  • an example of the present invention further provides a method for preparing the lithium ion battery separator 10, which includes the following steps:
  • a membrane substrate 110 having two opposing surfaces is provided, and the colloidal coating is applied to two opposite surfaces of the membrane substrate 110 to form two halloysite nanotube coatings 120.
  • the raw material of the halloysite nanotube 122 in the step S1 may be subjected to surface functionalization, and the surface functionalization treatment comprises the following steps:
  • the halloysite nanotube 122 is surface modified.
  • a certain amount of halloysite nanotubes 122 and deionized water may be mixed at a mass ratio of 10%, and then a molar concentration of 0.05% sodium hexametaphosphate is added, and the mixture is stirred at room temperature for about 30 minutes. Then, it was allowed to stand for 30 minutes, and halloysite aggregates and impurities were deposited on the bottom of the bottle and removed by filtration. The upper solution was collected by centrifugation, and the obtained halloysite nanotubes 122 were dried at 80 ° C for 24 hours under vacuum. The purified halloysite nanotubes 122 are further ground and sieved.
  • step S12 a certain amount of the purified halloysite nanotubes 122 in step S11 can be placed in a three-necked flask with a condensing device, an appropriate amount of solvent is added, and after ultrasonic dispersion for 30 minutes, 30 into the system. An inert gas is added for a minute, then an appropriate amount of a silane coupling agent is added and refluxed for 8 to 12 hours. The reaction suspension is centrifuged to obtain a solid phase, which is washed and dried to obtain a silane coupling agent surface-modified halloysite nanotube 122.
  • the solvent is one or more of ethanol, acetone, toluene, xylene, n-hexane, cyclohexane, tetrahydrofuran, dichloromethane, chloroform and N,N-dimethylformamide. .
  • step S12 the ultrasonically dispersed halloysite nanotubes 122, the ultrasonic cleaner used preferably has a power of 80 to 100 Hz.
  • the inert gas is one of high purity nitrogen gas and argon gas.
  • the silane coupling agent is one of CH 3 (CH 2 ) n SiX 3 , wherein n is 1 to 17, and the terminal hydrolyzable group X is an ethoxy group, a methoxy group or a chlorine group.
  • n 1 to 17
  • the terminal hydrolyzable group X is an ethoxy group, a methoxy group or a chlorine group.
  • the halloysite nanotubes 122 are dispersed in an organic solvent and surface-modified with a silane coupling agent.
  • the coupling agent is grafted to the surface of the halloysite nanotube 122 by a covalent bond, changing the properties of the halloysite surface.
  • the problem of agglomeration and dispersion between the halloysite nanotubes 122 is effectively solved.
  • the silane coupling agent modification process is simple and reliable.
  • the centrifugal separation in the method of separating the halloysite suspension by a centrifuge, preferably has a rotational speed of 4000 to 12000 r/min.
  • step S2 an appropriate amount of modified halloysite nanotubes 122 (having a diameter of 15 to 100 nm and a length of several hundred nanometers to several micrometers) is added to an appropriate amount of solvent, and ultrasonically stirred to uniformly disperse.
  • An appropriate amount of polymeric binder 124 is then added and stirred until the polymeric binder 124 dissolves to provide a halloysite nanotube coating gum.
  • the mass ratio of the polymer binder 124 to the halloysite nanotube 122 in the halloysite nanotube coating glue is between 0.1 and 0.4.
  • the solvent is one or two of tetrahydrofuran, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone.
  • the solvent is N,N-dimethylformamide.
  • the polymer binder 124 is one or two of polyurethane, polyvinylidene fluoride or polyimide.
  • the polymer binder 124 is polyimide.
  • step S2 the ultrasonically dispersed halloysite nanotubes 122, the ultrasonic cleaner used preferably has a power of 80 to 100 Hz.
  • the separator substrate 110 is one or two of the polyolefin separator Celgard series.
  • the diaphragm substrate 110 is Celgard 2325.
  • step S3 the halloysite nanotube coating 120, the thickness of both sides of the coating should be controlled from 3 micrometers to 5 micrometers.
  • the modified halloysite nanotubes are combined with a polymer binder to prepare a halloysite nanotube coating glue.
  • An halloysite nanotube composite coating was prepared by using a halloysite nanotube coating glue for the halloysite nanotube coating on the diaphragm substrate.
  • the scanning electron microscopy results in Fig. 4 show that the modified halloysite nanotubes are uniformly dispersed on the surface of the separator, and a nano-coat layer of non-woven fabric structure is formed under the constraint of the polymer, which effectively solves the diaphragm.
  • the thermal dimensional instability is maintained at 150 degrees Celsius for 1.5 hours, and the thermal contraction of the separator is less than 5%, which improves the safety of the battery.
  • the above results show that the natural halloysite nanotubes can effectively solve the problem of agglomeration and dispersibility after purification and surface modification, and can be used for ceramization modification of lithium battery separators, and effectively improve the thermal stability of the separator.
  • the natural halloysite has a wide source and low price, and the prepared halloysite nanocomposite separator has better toughness and thermal stability.
  • the composite separator prepared by the invention has broad application prospects in the field of lithium particle batteries.

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Abstract

一种锂离子电池隔膜（10），包括一隔膜基底（110）具有相对设置的两个表面、以及两个埃洛石纳米管涂层（120），所述两个埃洛石纳米管涂层（120）分别设置在所述隔膜基底（110）相对设置的两个表面。进一步提供所述锂离子电池隔膜（10）的制备方法。

Description

锂离子电池隔膜及其制备方法
相关申请
本发明申请要求2015年11月30日申请的，申请号为201510852200.4，名称为“一种锂离子电池隔膜及其制备方法”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本发明涉及电池技术领域，更具体地说，涉及一种电池隔膜及其制备方法。
背景技术
随着能源问题和环境污染的日益严重，新能源以及清洁能源逐渐得到重视。电化学的应用发展及新型储能电源的不断需求，使电池技术取得了很大的进步。锂离子电池具有高电压、高能量密度、循环寿命长以及无记忆效应等优势，使其广泛应用于笔记本电脑、手机、等便携式电子设备；同时，在航天技术、国防工业等方面具有广阔的应用前景，成为目前研究热点。
锂离子电池的关键部件主要有正极、负极、隔膜、电解液组成。其中隔膜作为锂离子电池的核心组成部件，其性能对电池的安全性能及电化学性能有重要影响。目前使用较多的是聚烯烃微孔膜，如聚丙烯(PP)膜、聚乙烯(PE)膜或两者的多层复合膜。虽然这些微孔聚烯烃隔膜具有良好的机械强度及化学稳定性，但因高温下易收缩、孔隙率低、保液率低等因素，影响锂离子电池的安全性能和使用寿命。为了改善隔膜的性能，可将耐高温的无机纳米颗粒涂覆在隔膜表面来增强电池隔膜的热尺寸稳定性及润湿性能。常用的无机纳米颗粒有Al2O3、SiO2和TiO2等，但因纳米颗粒的生产成本高、分散不均匀、易吸水等问题限制了其广泛应用。
发明内容
有鉴于此，确有必要提供一种成本低，粒子分散性好的锂离子电池复合隔膜及其制备方法。
一种锂离子电池隔膜，包括一隔膜基底以及两个埃洛石纳米管涂层，该隔膜基底具有相对设置的两个表面，所述两个埃洛石纳米管涂层分别设置在所述隔膜基底相对设置的两个表面。
所述隔膜基底为多孔结构，具有多个微孔。
所述两个埃洛石纳米管涂层涂覆于所述隔膜基底表面。
所述隔膜基底为聚烯烃微孔膜。
所述埃洛石纳米管涂层包括埃洛石纳米管以及聚合物粘合剂，所述埃洛石纳米管与所述聚合物粘合剂均匀混合，在一起形成所述埃洛石纳米管无纺布涂层。
所述聚合物粘合剂为聚氨酯，聚偏氟乙烯或聚酰亚胺中的一种或两种。
一种锂离子电池隔膜的制备方法，包括以下步骤：
S1，提供一埃洛石纳米管原料；
S2，提供一聚合物粘合剂及一溶剂，并将所述埃洛石纳米管原料及所述聚合物粘合剂分散在所述溶剂中，从而获得一埃洛石纳米管及聚合物粘合剂的涂层浆料；
S3，提供一具有两个相对表面的隔膜基底，将所述浆料分别涂覆在所述隔膜基底的两个相对表面形成两个埃洛石无纺布涂层。
步骤S1中，所述埃洛石纳米管原料为硅烷偶联剂改性的埃洛石纳米管。
步骤S2中，所述溶剂为四氢呋喃、三氯甲烷、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺或N-甲基吡咯烷酮的一种或两种。
步骤S2中，所述聚合物粘合剂为聚氨酯，聚偏氟乙烯或聚酰亚胺中的一种。
本发明使用硅烷偶联剂对埃洛石纳米管进行表面改性，并利用溶液共混法使其与粘合剂聚合物混合制备隔膜涂层浆料，用于对锂电隔膜的陶瓷化改性，从而提高锂离子电池的热稳定性及相应的电化学性能。埃洛石纳米管(HNTs)是一种价格低廉的天然纳米管，是双层1:1型铝硅酸盐，其分子式为Al2SiO5(OH)·nH2O(n＝0或2)，具有典型结晶结构，常为多壁管状结构，由内层铝氧八面体和外层的硅氧四面体晶格错位卷曲而成，其层间存在结晶水，且内外表面有硅羟基和铝羟基团存在。埃洛石纳米管具有独特的管状结构，管长为1～15微米，管径在10～50纳米之间，可以与聚合物复合，制备优良的聚合物/无机纳米复合材料。
附图说明
图1为本发明实施例提供的锂离子电池隔膜的结构示意图。
图2为图1中的锂离子电池隔膜中的埃洛石纳米管涂层的放大结构示意图。
图3为本发明实施例提供的锂离子电池隔膜中的表面修饰后的埃洛石纳米管材料的扫描电镜照片。
图4为图1中的埃洛石纳米管材料构成的埃洛石纳米管涂层的扫描电镜照片。
图5为本发明实施例提供的锂离子电池用隔膜的制备方法的流程图。
主要元件符号说明
锂离子电池用隔膜  10
隔膜基底  110
埃洛石纳米管涂层  120
埃洛石纳米管  122
聚合物粘合剂  124
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
下面结合附图和实施例对本发明作进一步的阐述，参照附图。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
请参阅图1，本发明实施例提供一种锂离子电池用隔膜10，其包括一隔膜基底110，以及两个埃洛石纳米管涂层120。所述隔膜基底110为一平面结构，是具有一定厚度的薄膜。所述隔膜基底110具有两个相对表面，所述两个埃洛石纳米管涂层120分别设置在所述隔膜基底110的两个相对表面。
所述隔膜基底110为聚烯烃微孔膜，如聚丙烯(PP)膜、聚乙烯(PE)膜或两者的多层复合膜。所述隔膜基底110具有多个微孔，所述两个埃洛石纳米管涂层120覆盖在多孔膜的表面。本实施例中，所述隔膜基底110为聚乙烯(PE)膜，厚度为25微米。
请参见图2，所述埃洛石纳米管涂层120包括多个埃洛石纳米管122、以及聚合物粘合剂124，所述多个埃洛石纳米管122与所述聚合物粘合剂124复合在一起形成所述埃洛石纳米管涂层120。所述聚合物粘合剂124为聚氨酯，聚偏氟乙烯或聚酰亚胺的一种或两种。本实施例中，所述聚合物粘合剂124为聚酰亚胺。
请参见图3，所述埃洛石纳米管122可以为功能化的埃洛石纳米管，可以用硅烷偶联剂对埃洛石纳米管进行表面修饰，所述硅烷偶联剂通过共价键接枝到所述埃洛石纳米管122的表面。所述埃洛石纳米管122经过表面修饰以后，所述聚合物粘合剂124均匀分散在所述埃洛石纳米管涂层120中。进一步地，请参见图4，所述埃洛石纳米管122可以均匀地分散在所述隔膜基底110的两个相对表面。可以理解，所述埃洛石纳米管122功能化处理的不限于表面修饰，现有技术中有利于埃洛石纳米管122分散的功能化处理方法均适用于本发明。
请参见图5，本发明实例进一步提供所述锂离子电池隔膜10的制备方法，其包括以下步骤：
S1，提供一埃洛石纳米管122的原料；
S2，提供一聚合物粘合剂124及一溶剂，并将所述埃洛石纳米管122的原料及所述聚合 物粘合剂分散在所述溶剂中，从而获得一埃洛石纳米管122及聚合物粘合剂124构成涂层浆料；
S3，提供一具有两个相对表面的隔膜基底110，将所述胶体涂料涂覆在所述隔膜基底110的两个相对表面形成两个埃洛石纳米管涂层120。
步骤S1中所述埃洛石纳米管122的原料可以经过表面功能化处理，所述表面功能化处理包括以下步骤：
S11，对埃洛石纳米管122的原料进行提纯；以及
S12，将所述埃洛石纳米管122进行表面改性。
步骤S11中，可以将一定量的埃洛石纳米管122与去离子水按照10％的质量比混合，然后再加入埃洛石质量分数0.05％的六偏磷酸钠，于室温下搅拌约30分钟，然后静置30分钟，埃洛石聚集体和杂质沉积在瓶子的底部，通过过滤去除。上层溶液通过离心收集，将得到的埃洛石纳米管122于80摄氏度温度下，真空干燥24小时。纯化后的埃洛石纳米管122再进行研磨、过筛。
步骤S12中，可以取一定量的步骤S11中纯化后的埃洛石纳米管122置入带有冷凝装置的三口瓶中，加入适量的溶剂，经超声分散30分钟后，向体系里通入30分钟惰性气体，然后加入适量的硅烷偶联剂，回流8～12小时。反应后的悬浮液经离心分离后得到固相，该固相经洗涤和干燥，从而获得硅烷偶联剂表面修饰过的埃洛石纳米管122。
步骤S12中，所述的溶剂为乙醇、丙酮、甲苯、二甲苯、正己烷、环己烷、四氢呋喃、二氯甲烷、氯仿及N，N-二甲基甲酰胺等中的一种或多种。
步骤S12中，所述的超声分散埃洛石纳米管122，所用的超声波清洗器优选功率在80～100Hz。
步骤S12中，所述的惰性气体为高纯氮气、氩气中的一种。
步骤S12中，所述的硅烷偶联剂为CH3(CH2)nSiX3中的一种，其中n为1～17，末端可水解基团X为乙氧基、甲氧基、氯基、甲氧基乙氧基、乙酰氧基等中的一种。埃洛石纳米管122分散到有机溶剂中，用硅烷偶联剂对其进行表面修饰，偶联剂通过共价键接枝到埃洛石纳米管122的表面，改变了埃洛石表面的性质，有效的解决了埃洛石纳米管122间的团聚和分散问题。且硅烷偶联剂改性工艺简单、可靠。
步骤S12中，所述采用离心机分离埃洛石悬浊液的方法中，离心分离优选转速为4000～12000r/min。
步骤S2中，将适量改性后的埃洛石纳米管122(管径15～100纳米，管长几百纳米到几微米)，加入适量的溶剂，经超声，搅拌使其均匀分散。然后加入适量的聚合物粘合剂124，搅拌至该聚合物粘合剂124溶解，得到埃洛石纳米管涂层胶液。
步骤S2中，所述的埃洛石纳米管涂层胶液中，聚合物粘合剂124与埃洛石纳米管122的质量比为0.1～0.4之间。
步骤S2中，所述的溶剂为四氢呋喃、三氯甲烷、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或N-甲基吡咯烷酮的一种或两种。本实施例中，所述溶剂为N,N-二甲基甲酰胺。
步骤S2中，所述的聚合物粘合剂124为聚氨酯，聚偏氟乙烯或聚酰亚胺的一种或两种。本实施例中，所述聚合物粘合剂124为聚酰亚胺。
步骤S2中，所述的超声分散埃洛石纳米管122，所用的超声波清洗器优选功率在80～100Hz。
步骤S3中，所述的隔膜基底110为聚烯烃隔膜Celgard系列中的一种或两种。本实例中，所述隔膜基底110为Celgard 2325。
步骤S3中，所述的埃洛石纳米管涂层120，涂层两面的厚度应控制在3微米至5微米。
实例1：
称取5g纯化的埃洛石纳米管置入带有冷凝装置的三口瓶中，加入250毫升乙醇溶剂，经超声分散30分钟后，向体系里通入30分钟惰性气体，去除纳米管表面吸附的氧气，然后加入2.5毫升的十八烷基三乙氧基硅烷偶联剂，回流8～12小时，停止反应。反应后的悬浮液经离心分离后得到固相，使用乙醇或丙酮洗涤，最后进行干燥，得到改性后的埃洛石纳米管。
取1克改性后的埃洛石纳米管，加入10毫升的N，N-二甲基甲酰胺，经超声，搅拌使其均匀分散。然后加入0.185克的聚酰亚胺粘合剂，搅拌至聚合物溶解，得到涂层胶液；将涂层胶液涂覆于25微米厚的微孔Celgard 2325隔膜(孔隙率＞35％)两侧，总涂覆厚度控制在3～5微米，然后将涂覆好的隔膜于60℃下干燥24小时，得到埃洛石纳米管复合涂层隔膜，即埃洛石无纺布陶瓷化隔膜。
实施例2：
称取5g纯化的埃洛石纳米管置入带有冷凝装置的三口瓶中，加入250毫升乙醇溶剂，经超声分散30分钟后，向体系里通入30分钟惰性气体，驱逐纳米管表面吸附的氧气，然后加入2.5毫升的十二烷基三乙氧基硅烷偶联剂，回流8～12小时，停止反应。反应后的悬浮液经离心分离后得到固相，使用乙醇或丙酮洗涤，最后进行干燥，得到改性后的埃洛石纳米管。
取1克改性后的埃洛石纳米管，加入10毫升的N，N-二甲基甲酰胺，经超声，搅拌使其均匀分散。然后加入0.185克的聚酰亚胺粘合剂，搅拌至聚合物溶解，得到涂层胶液；将涂层胶液涂覆于25微米厚的微孔Celgard 2325隔膜(孔隙率＞35％)两侧，总涂覆厚度控制在3～5微米，然后将涂覆好的隔膜于60℃下干燥24小时，得到埃洛石纳米管复合涂层隔膜，即埃洛石无纺布陶瓷化隔膜。
本发明将改性后的埃洛石纳米管与聚合物粘合剂复合，制备了埃洛石纳米管涂层胶液， 并将埃洛石纳米管涂层胶液用于隔膜基底的埃洛石纳米管涂层，制备了埃洛石纳米管复合隔膜。图4中的扫面电子显微镜结果表明，改性后的埃洛石纳米管均匀分散在隔膜的表面，在聚合物的束缚下形成了一层无纺布结构的纳米涂层，有效解决了隔膜热尺寸不稳定性，在150摄氏度条件下保温1.5小时，隔膜的热收缩小于5％，提高了电池的安全性。以上的结果说明天然埃洛石纳米管经纯化、表面改性后，有效的解决了团聚及分散性问题，可用于对锂电池隔膜的陶瓷化改性，有效的提高了隔膜的热稳定性。天然埃洛石来源广、价格低，制备所得的埃洛石纳米复合隔膜具有较好的韧性和热稳定性，本发明制备的复合隔膜在锂粒子电池领域具有广阔的应用前景。
另外，本领域技术人员还可在本发明精神内作其它变化，当然这些依据本发明精神所作的变化，都应包含在本发明所要求保护的范围内。

Claims (10)

  1. 一种锂离子电池隔膜，其特征在于，包括一隔膜基底以及两个埃洛石纳米管涂层，该隔膜基底具有相对设置的两个表面，所述两个埃洛石纳米管涂层分别设置在所述隔膜基底相对设置的两个表面。
  2. 如权利要求1所述的锂离子电池隔膜，其特征在于，所述隔膜基底为多孔结构，具有多个微孔。
  3. 如权利要求2所述的锂离子电池隔膜，其特征在于，所述两个埃洛石纳米管涂层涂覆在所述隔膜基底的表面。
  4. 如权利要求2所述的锂离子电池隔膜，其特征在于，所述隔膜基底为聚烯烃微孔膜。
  5. 如权利要求1所述的锂离子电池隔膜，其特征在于，所述埃洛石纳米管涂层包括多个埃洛石纳米管、以及聚合物粘合剂，所述多个埃洛石纳米管与所述聚合物粘合剂混合在一起形成所述埃洛石纳米管无纺布涂层。
  6. 如权利要求5所述的锂离子电池隔膜，其特征在于，所述聚合物粘合剂为聚氨酯，聚偏氟乙烯或聚酰亚胺的一种或两种。
  7. 一种锂离子电池隔膜的制备方法，包括以下步骤：
    S1，提供一埃洛石纳米管原料；
    S2，提供一聚合物粘合剂及一溶剂，并将所述埃洛石纳米管原料及所述聚合物粘合剂分散在所述溶剂中，从而获得一埃洛石纳米管及聚合物粘合剂涂层浆料；以及
    S3，提供一具有两个相对表面的隔膜基底，将所述浆料涂覆在所述隔膜基底的两个相对表面形成两个埃洛石纳米管涂层。
  8. 如权利要求7所述的锂离子电池隔膜的制备方法，其特征在于，步骤S1中，所述埃洛石纳米管原料为硅烷偶联剂改性后的埃洛石纳米管。
  9. 如权利要求7所述的锂离子电池隔膜的制备方法，其特征在于，步骤S2中，所述溶剂为四氢呋喃、三氯甲烷、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺或N-甲基吡咯烷酮的一种或两种。
  10. 如权利要求7所述的锂离子电池隔膜的制备方法，其特征在于，步骤S2中，所述聚合物粘合剂为聚氨酯，聚偏氟乙烯或聚酰亚胺的一种或两种。
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