WO2017124714A1 - 一种mfi型沸石涂覆锂离子电池隔膜的制备方法 - Google Patents

一种mfi型沸石涂覆锂离子电池隔膜的制备方法 Download PDF

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WO2017124714A1
WO2017124714A1 PCT/CN2016/090620 CN2016090620W WO2017124714A1 WO 2017124714 A1 WO2017124714 A1 WO 2017124714A1 CN 2016090620 W CN2016090620 W CN 2016090620W WO 2017124714 A1 WO2017124714 A1 WO 2017124714A1
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mfi
lithium ion
ion battery
preparing
mfi zeolite
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French (fr)
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林跃生
董学良
金翼
张遥骋
傅凯
刘曙光
闫雪生
褚永金
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China Electric Power Research Institute Co Ltd CEPRI
North China Branch of State Grid Corp of China
State Grid Corp of China SGCC
Arizona State University ASU
Arizona State University Downtown Phoenix campus
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China Electric Power Research Institute Co Ltd CEPRI
North China Branch of State Grid Corp of China
State Grid Corp of China SGCC
Arizona State University ASU
Arizona State University Downtown Phoenix campus
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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
    • 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
    • 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
    • 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
    • H01M50/443—Particulate 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
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • 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 preparation method of a lithium ion battery separator, in particular to a preparation method of a MFI zeolite coated lithium ion battery separator.
  • Lithium-ion batteries have become the main power source for all kinds of portable electronic products due to their high working voltage, high energy density, no memory effect, long cycle life and low self-discharge.
  • the “Energy Conservation and New Energy Vehicle Industry Development Plan” formulated by the state has played a powerful role in promoting the rapid development of lithium-ion batteries and related materials.
  • the lithium ion battery is mainly composed of a positive electrode, a negative electrode, an electrolyte and a diaphragm.
  • the separator is a key material for lithium-ion batteries.
  • commercial lithium-ion membranes are mainly made of polyethylene and polypropylene microporous membranes, but they cannot be used in the field of power lithium-ion batteries due to the limitations of the nature of the membrane materials.
  • the membrane must absorb and retain a certain amount of liquid electrolyte to achieve low internal resistance, high ionic conductivity.
  • the rapid absorption of the electrolyte by the diaphragm greatly affects the filling of the diaphragm electrolyte during battery assembly.
  • Commercially available polyolefin separators with commonly used electrolytes such as ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC) and dimethyl carbonate due to low surface energy and non-polarity ( DMC) has poor wettability. Poor wetting results in high internal impedance and poor electrochemical performance, which greatly inhibits the transport of lithium ions. This has become a major obstacle to energy storage equipment, high-energy electric vehicles and smart grid applications.
  • the diaphragm must be able to withstand sufficient tension during assembly and winding of the battery and have high puncture resistance.
  • Polyolefin separators generally have high tensile strength but low puncture strength.
  • lithium metal inevitably forms dendrites at the anode. Lithium dendrites can penetrate the polyolefin membrane causing a short circuit. This converts all stored chemical energy into heat, which causes smoke and further causes a fire.
  • the object of the present invention is to overcome the problems of poor wettability, low puncture resistance and poor safety of the lithium ion battery separator and the electrolyte in the prior art described above, and to provide a strong wettability, high puncture strength and good safety performance.
  • the present invention adopts the following technical solutions:
  • a method for preparing a MFI-type zeolite coated lithium ion battery separator comprising the following steps:
  • MFI zeolite preparing a silica-alumina composite precursor or a pure silica precursor, and washing the prepared precursor with deionized water through a centrifuge, drying at room temperature, and then calcining at a high temperature;
  • binder Polyvinylidene fluoride powder, nitrogen-nitrodimethylformamide and methyl ethyl ketone are prepared in a ratio of 1:1 to 50:1 to 50 by mass ratio, and the mixture is stirred for 5 to 10 minutes. mixture;
  • MFI zeolite coating suspension Preparation of MFI zeolite coating suspension: mixing the MFI zeolite of step 1), the binder of step 2) and methyl ethyl ketone in a ratio of 1 to 10:1 to 100:1 to 1000 by mass. The liquid is dispersed by ultrasonic wave for 1 to 1000 minutes, and then stirred for 1 to 100 hours to obtain a uniform and stable MFI zeolite coating suspension;
  • MFI zeolite coated membrane after step 3) MFI zeolite coating suspension impregnation polymer membrane for 5 ⁇ 100s, cooling for 1 ⁇ 1000min; repeat the above operation 1 ⁇ 1000 times, the coating quality is uniform MFI zeolite coated membrane;
  • MFI zeolite-coated membrane Treatment of MFI zeolite-coated membrane: The MFI zeolite-coated membrane of step 4) was dried at 30-90 ° C for 10 to 100 h, and the membrane was smoothed during the drying process without wrinkles and bending.
  • the preparation of the silicon-aluminum composite precursor in the step 1) comprises: deionized water, sodium hydroxide, tetrabutylammonium bromide, Al 2 (SO 4 ) 3 ⁇ 18H 2 O and tetraethyl silicate
  • the mixture is prepared according to the ratio of mass ratio of 60:0.27:1.77:0 to 0.4:6.2, stirred for 5-20 min, and maintained at 160-180 ° C for 10-12 h to obtain a silicon-aluminum composite precursor.
  • the preparation of the pure silica precursor in the step 1) comprises: ratio of the silica powder, the sodium hydroxide and the tetrapropylamine hydroxide in a mass ratio of 90 to 110:5 to 10:20 to 30.
  • the mixture is prepared, stirred for 5-20 min, and kept at 100-150 ° C for 10-15 h to obtain a pure silica precursor.
  • the preparation of the pure silica precursor is: preparing a mixture of silica powder, sodium hydroxide and tetrapropylammonium hydroxide at a mass ratio of 100:7:30, stirring for 10 min, 120 ° C After holding for 12 h, a pure silica precursor was obtained.
  • the optimal conditions for the high temperature calcination in the step 1) are: calcination at 550 ° C for 8 h.
  • the silica has a particle size of 5 nm to 1 ⁇ m; the MFI zeolite has a silicon-aluminum content ratio of not less than 1:1; and the MFI-type zeolite coating has a thickness of 0.1 ⁇ m to 300 ⁇ m;
  • the prepared MFI-type zeolite-coated lithium ion battery separator has a thickness of from 10 ⁇ m to 500 ⁇ m.
  • the polymer separator is polyethylene, polypropylene or polyimide.
  • the technical solution provided by the invention has simple preparation process, convenient operation, continuous production on the production line, strong practicability and low production cost.
  • the MFI zeolite coated lithium ion battery separator prepared by the technical solution provided by the invention is applied to a lithium battery, so that the battery can significantly improve its safety performance, charge and discharge cycle life and heat resistance.
  • the MFI zeolite coating can better fill the pores of the membrane in the technical solution provided by the invention, so that the MFI zeolite coated lithium ion battery separator has strong wettability with the electrolyte.
  • the MFI zeolite-coated lithium ion battery separator prepared by the technical solution provided by the invention has high puncture resistance and is more than twice of the puncture strength of the commercial polyolefin separator.
  • Figure 1 (a1) ZCPP25 surface (silicon-aluminum content ratio 25:1), (a2) ZCPP25 cross-section (silicon-aluminum content ratio 25:1), (b1) ZCPP50 surface (silicon-aluminum content ratio 50:1), (b2) ZCPP50 cross section (silicon-aluminum content ratio 50:1), (c1) ZCPP100 surface (silicon-aluminum content ratio 100:1), (c2) ZCPP100 cross-section (silicon-aluminum content ratio 100:1), (d1 ZCPP200 surface (silicon-aluminum content ratio 200:1), (d2) ZCPP200 cross-section (silicon-aluminum content ratio 200:1), (e1) SCPP surface (excluding aluminum element) and (e2) SCPP cross section (excluding Scanning electron micrograph of aluminum element) MFI zeolite coated membrane;
  • Figure 2 (a) ZCPP25 (silicon-aluminum content ratio of 25:1), ZCPP50 (silicon-aluminum content ratio of 50:1), ZCPP100 (silicon-aluminum content ratio of 100:1), ZCPP200 (silicon-aluminum content ratio of 200: 1) a graph of the contact angle of the MFI zeolite coated membrane with the electrolyte as a function of time;
  • Figure 3 ZCPP25 (aluminum-aluminum content ratio of 25:1) MFI zeolite coated membrane and PP (poly Comparison of propylene) commercial polymer membrane infiltration.
  • a preparation method of a MFI zeolite coated lithium ion battery separator comprising the following steps:
  • MFI zeolite Preparation of MFI zeolite: Preparation of silica-alumina composite precursor, deionized water, sodium hydroxide, tetrabutylammonium bromide, Al 2 (SO 4 ) 3 ⁇ 18H 2 O and tetraethyl silicate The mixture was prepared by mixing the mixture at a mass ratio of 60:0.27:1.77:0.4:6.2, stirring for 10 min, and holding at 175 ° C for 12 h to obtain a silica-alumina composite precursor.
  • the precursor prepared above was washed with deionized water in a centrifuge to wash the prepared precursor, dried at room temperature, and then calcined at 550 ° C for 8 h.
  • binder Polyvinylidene fluoride powder, nitrogen-nitrodimethylformamide and methyl ethyl ketone were prepared in a ratio of 1:16:16 by mass ratio, and stirred for 10 minutes to obtain a binder;
  • MFI zeolite coating suspension The mixture of the MFI zeolite of step 1), the binder of step 2) and methyl ethyl ketone is prepared at a mass ratio of 1:4:30, and dispersed by ultrasonic for 30 min. After stirring for 5 h, a uniformly stable MFI zeolite coating suspension is obtained;
  • MFI zeolite coated membrane was dried for 12 h at 60 ° C, and the membrane was smoothed during the drying process without wrinkles and buckling.
  • a preparation method of a MFI zeolite coated lithium ion battery separator comprising the following steps:
  • MFI zeolite Preparation of MFI zeolite: Preparation of silica-alumina composite precursor, deionized water, sodium hydroxide, tetrabutylammonium bromide, Al 2 (SO 4 ) 3 ⁇ 18H 2 O and tetraethyl silicate The mixture was prepared in a mass ratio of 60:0.27:1.77:0.2:6.2, stirred for 5 min, and kept at 180 ° C for 12 h to obtain a silica-alumina composite precursor.
  • the precursor prepared above was washed with deionized water in a centrifuge to wash the prepared precursor, dried at room temperature, and then calcined at 550 ° C for 8 h.
  • binder Polyvinylidene fluoride powder, nitrogen-nitrodimethylformamide and methyl ethyl ketone were prepared in a ratio of 1:30:25 by mass ratio, and the binder was obtained after stirring for 8 minutes;
  • MFI zeolite coating suspension The MFI zeolite of step 1), the binder of step 2) and methyl ethyl ketone are prepared in a ratio of 3:15:20 by mass, and dispersed by ultrasonic wave for 25 min. After stirring for 4 h, a uniformly stable MFI zeolite coating suspension is obtained;
  • MFI zeolite coated membrane was dried at 90 ° C for 15 h, and the membrane was smoothed during the drying process without wrinkles and buckling.
  • a preparation method of a MFI zeolite coated lithium ion battery separator comprising the following steps:
  • MFI zeolite Preparation of MFI zeolite: Preparation of silica-alumina composite precursor, deionized water, sodium hydroxide, tetrabutylammonium bromide, Al 2 (SO 4 ) 3 ⁇ 18H 2 O and tetraethyl silicate The mixture was prepared in a mass ratio of 60:0.27:1.77:0.1:6.2, stirred for 10 min, and kept at 160 ° C for 10 h to obtain a silica-alumina composite precursor.
  • the precursor prepared above was washed with deionized water in a centrifuge to wash the prepared precursor, dried at room temperature, and then calcined at 550 ° C for 8 h.
  • binder Polyvinylidene fluoride powder, nitrogen-nitrodimethylformamide and methyl ethyl ketone were prepared in a ratio of 1:25:20 by mass ratio, and stirred for 8 minutes to obtain a binder;
  • MFI zeolite coating suspension The MFI zeolite of step 1), the binder of step 2) and methyl ethyl ketone are prepared in a ratio of 10:30:20 by mass, and dispersed by ultrasonic for 300 min. After stirring for 60 h, a uniformly stable MFI zeolite coating suspension is obtained;
  • MFI zeolite coated membrane was dried at 50 ° C for 20 h, and the membrane was flattened during the drying process without wrinkles and buckling.
  • a preparation method of a MFI zeolite coated lithium ion battery separator comprising the following steps:
  • MFI zeolite Preparation of MFI zeolite: Preparation of silica-alumina composite precursor, deionized water, sodium hydroxide, tetrabutylammonium bromide, Al 2 (SO 4 ) 3 ⁇ 18H 2 O and tetraethyl silicate The mixture was prepared in a mass ratio of 60:0.27:1.77:0.05:6.2, stirred for 14 min, and kept at 170 ° C for 12 h to obtain a silica-alumina composite precursor.
  • the precursor prepared above was washed with deionized water in a centrifuge to wash the prepared precursor, dried at room temperature, and then calcined at 550 ° C for 8 h.
  • binder Polyvinylidene fluoride powder, nitrogen-nitrodimethylformamide and methyl ethyl ketone are prepared in a ratio of 1:50:50 by mass ratio, and stirred for 10 minutes to obtain a binder;
  • MFI zeolite coating suspension The mixture of the MFI zeolite of step 1), the binder of step 2) and methyl ethyl ketone is prepared at a mass ratio of 8:20:40, and dispersed by ultrasonic for 500 min. After stirring for 3 h, a uniform and stable MFI zeolite coating suspension is obtained;
  • MFI zeolite coated membrane was dried at 40 ° C for 25 h, and the membrane was smoothed during the drying process without wrinkles and buckling.
  • a preparation method of a MFI zeolite coated lithium ion battery separator comprising the following steps:
  • MFI-type zeolite preparing a pure silica precursor, preparing a mixture of silica powder, sodium hydroxide and tetrapropylamine at a mass ratio of 100:7:30, and stirring for 15 minutes. The mixture was kept at 120 ° C for 12 h to obtain a pure silica precursor.
  • the precursor prepared above was washed with deionized water in a centrifuge to wash the prepared precursor, dried at room temperature, and then calcined at 550 ° C for 8 h.
  • binder Polyvinylidene fluoride powder, nitrogen-nitrodimethylformamide and methyl ethyl ketone were prepared in a ratio of 1:20:15 by mass ratio, and stirred for 7 minutes to obtain a binder;
  • MFI zeolite coating suspension The MFI zeolite of step 1), the binder of step 2) and methyl ethyl ketone are prepared in a ratio of 4:8:20 by mass, and dispersed by ultrasonic for 400 min. After stirring for 10 h, a uniform and stable MFI zeolite coating suspension is obtained;
  • step 4) Preparation of MFI zeolite coated membrane: using step 3) MFI zeolite coating suspension infiltration high score After the sub-membrane is 20 s, it is cooled for 350 min; the above operation is repeated 15 times to obtain a MFI zeolite-coated separator having a uniform coating quality;
  • MFI zeolite coated membrane was dried at 70 ° C for 18 h, and the membrane was smoothed during the drying process without wrinkles and buckling.

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Abstract

一种MFI型沸石涂覆锂离子电池隔膜的制备方法，该制备方法包括将已制备的MFI型沸石、粘合剂和丁酮按质量比为1～10：1～100：1～1000的比例配制混合液，经超声波处理后得涂覆悬浊液；用MFI沸石涂覆悬浊液浸渗高分子隔膜，得涂层质量均匀的MFI沸石涂覆的隔膜；并在30～90℃下，将所得的MFI沸石涂覆的隔膜烘干。该技术方案制备工艺简单，便于操作，生产线上能连续生产，实用性强，生产成本低，提高电池的安全性能、充放电循环寿命及耐热性；MFI型沸石涂覆锂离子电池隔膜与电解液之间有很强的湿润性；且MFI型沸石涂覆锂离子电池隔膜抗穿刺强度高，是聚烯烃隔膜抗穿刺强度的2倍以上。

Description

一种MFI型沸石涂覆锂离子电池隔膜的制备方法 技术领域
本发明涉及一种锂离子电池隔膜的制备方法，具体讲，涉及一种MFI型沸石涂覆锂离子电池隔膜的制备方法。
背景技术
因具有工作电压高、能量密度大、无记忆效应、循环寿命长和自放电低等优点，锂离子电池已成为各类便携电子产品的主力电源。国家制定的《节能与新能源汽车产业发展规划》，为锂离子电池及相关材料快速发展起到了强大的推动作用。
锂离子电池主要由正极、负极、电解液及隔膜四部分组成。隔膜是锂离子电池的关键材料，当前商品化的锂电隔膜以聚乙烯和聚丙烯微孔膜为主，但由于膜材料本身性质的限制而无法应用于动力锂离子电池领域。
隔膜必须吸收和保持一定量的液体电解质以实现低内阻、高离子电导率。隔膜能快速吸收电解液在电池组装的过程中极大影响着隔膜电解液的填充。因低表面能和非极性，使得商品化的聚烯烃隔膜与常用的电解液如碳酸亚乙酯(EC)、碳酸丙烯酯(PC)、碳酸二乙酯(DEC)和碳酸二甲酯(DMC)间润湿性较差。较差的润湿性导致隔膜内部阻抗较高、电化学性能较差，极大地抑制了锂离子的传输。这成为能源储备设备、高能量电动汽车和智能电网应用的极大障碍。
另外，隔膜在电池组装卷绕过程中必须能承受足够的张力并对电极具备高的抗穿刺强度。聚烯烃隔膜通常抗拉伸强度高但是抗穿刺强度较低。在大电流充电或者多次循环的情况下，锂金属不可避免的在阳极形成枝晶。锂枝晶可以穿透聚烯烃隔膜造成短路。这会将所有储存的化学能转化成热能，导致烟雾并进一步造成起火爆炸。
因此，需要提供一种针对上述现有技术不足的改进技术方案。
发明内容
本发明的目的是克服上述现有技术中锂离子电池隔膜和电解液湿润性差、抗穿刺强度低、安全性差等方面的问题，提供一种具有较强湿润性、抗穿刺强度高、安全性能好、充放电循环寿命长及耐热性好的MFI型沸石涂覆锂离子电池隔膜的制备方法。
为实现上述目的，本发明采用以下技术方案：
一种MFI型沸石涂覆锂离子电池隔膜的制备方法，所述制备方法包括如下步骤：
1)MFI型沸石的制备：制备硅铝复合前驱体或纯氧化硅前驱体，经离心机用去离子水清洗已制备的前驱体，室温晾干后再高温煅烧；
2)粘合剂的制备：聚偏氟乙烯粉末、氮氮二甲基甲酰胺和丁酮按质量比为1：1～50：1～50的比例配制混合液，搅拌5～10min后得粘合剂；
3)MFI沸石涂覆悬浊液的制备：将步骤1)的MFI型沸石、步骤2)的粘合剂和丁酮按质量比为1～10：1～100：1～1000的比例配制混合液，经超声波分散1～1000min后，搅拌1～100h，得均匀稳定的MFI型沸石涂覆悬浊液；
4)MFI沸石涂覆的隔膜的制备：用步骤3)MFI沸石涂覆悬浊液浸渗高分子隔膜5～100s后，冷却1～1000min；重复上述操作1～1000次，得涂层质量均匀的MFI沸石涂覆的隔膜；
5)MFI沸石涂覆的隔膜的处理：30～90℃下，将步骤4)的MFI沸石涂覆的隔膜烘干10～100h，且烘干过程中使隔膜平整，无褶皱和弯折。
进一步的，所述步骤1)中制备硅铝复合前驱体包括：将去离子水、氢氧化钠、四丁基溴化铵、Al2(SO4)3·18H2O和硅酸四乙酯按质量比为60：0.27：1.77：0～0.4：6.2的比例配制混合液，搅拌5～20min，160～180℃保温10～12h，得硅铝复合前驱体。
进一步的，所述步骤1)中制备纯氧化硅前驱体包括：将二氧化硅粉末、氢氧化钠和氢氧化四丙基胺按质量比为90～110：5～10：20～30的比例配制混合液，搅拌5～20min，100～150℃保温10～15h，得纯氧化硅前驱体。
进一步的，所述的制备纯氧化硅前驱体为：将二氧化硅粉末、氢氧化钠和四丙基氢氧化铵按质量比为100：7：30的比例配制混合液，搅拌10min，120℃保温12h，得纯氧化硅前驱体。
进一步的，所述步骤1)中所述高温煅烧的最优条件为：550℃下煅烧8h。
进一步的，所述的二氧化硅粒径大小为5nm-1μm；所述MFI型沸石中硅铝元素含量比例为不小于1:1；所述MFI型沸石涂覆层厚度为0.1μm-300μm；所制备的MFI型沸石涂覆的锂离子电池隔膜厚度为10μm-500μm。
进一步的，所述的高分子隔膜为聚乙烯、聚丙烯或聚酰亚胺。
与最接近的现有技术相比，本发明提供的技术方案具有如下优异效果：
1、本发明提供的技术方案制备工艺简单，便于操作，生产线上能连续生产，实用性强，生产成本低。
2、本发明提供的技术方案制备的MFI型沸石涂覆锂离子电池隔膜应用于锂电池中，使电池能显著提高其安全性能、充放电循环寿命及耐热性。
3、本发明提供的技术方案中MFI型沸石涂层能更好的填充隔膜的空隙，使MFI型沸石涂覆锂离子电池隔膜与电解液之间有很强的湿润性。
4、本发明提供的技术方案制备的MFI型沸石涂覆锂离子电池隔膜抗穿刺强度高，是商品聚烯烃隔膜抗穿刺强度的2倍以上。
附图说明
为了更清楚地说明本发明中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1(a1)ZCPP25表面(硅铝元素含量比25:1)、(a2)ZCPP25截面(硅铝元素含量比25:1)、(b1)ZCPP50表面(硅铝元素含量比50:1)、(b2)ZCPP50截面(硅铝元素含量比50:1)、(c1)ZCPP100表面(硅铝元素含量比100:1)、(c2)ZCPP100截面(硅铝元素含量比100:1)、(d1)ZCPP200表面(硅铝元素含量比200:1)、(d2)ZCPP200截面(硅铝元素含量比200:1)、(e1)SCPP表面(不含铝元素)和(e2)SCPP截面(不含铝元素)MFI型沸石涂覆隔膜的扫描电子显微镜图；
图2(a)ZCPP25(硅铝元素含量比25:1)、ZCPP50(硅铝元素含量比50:1)、ZCPP100(硅铝元素含量比100:1)、ZCPP200(硅铝元素含量比200:1)的MFI型沸石涂覆隔膜与电解液接触角随时间变化图；
(b)SCPP(不含铝元素)的MFI型沸石涂覆隔膜与PP(聚丙烯)商品化高分子隔膜接触角对比；
图3ZCPP25(硅铝元素含量比25:1)的MFI型沸石涂覆隔膜和PP(聚 丙烯)商品化高分子隔膜浸润情况对比图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
一种MFI型沸石涂覆锂离子电池隔膜的制备方法，制备方法包括如下步骤：
1)MFI型沸石的制备：制备硅铝复合前驱体为，将去离子水、氢氧化钠、四丁基溴化铵、Al2(SO4)3·18H2O和硅酸四乙酯按质量比为60：0.27：1.77：0.4：6.2的比例配制混合液，搅拌10min，175℃保温12h，得硅铝复合前驱体。
将上述制备的前驱体经离心机用去离子水清洗已制备的前驱体，室温晾干后再550℃下煅烧8h。
2)粘合剂的制备：聚偏氟乙烯粉末、氮氮二甲基甲酰胺和丁酮按质量比为1：16：16的比例配制混合液，搅拌10min后得粘合剂；
3)MFI沸石涂覆悬浊液的制备：将步骤1)的MFI型沸石、步骤2)的粘合剂和丁酮按质量比为1：4：30的比例配制混合液，经超声波分散30min后，搅拌5h，得均匀稳定的MFI型沸石涂覆悬浊液；
4)MFI沸石涂覆的隔膜的制备：用步骤3)MFI沸石涂覆悬浊液浸渗高分子隔膜5s后，冷却180min；重复上述操作5次，得涂层质量均匀的MFI沸石涂覆的隔膜；
5)MFI沸石涂覆的隔膜的处理：60℃下，将步骤4)的MFI沸石涂覆的隔膜烘干12h，且烘干过程中使隔膜平整，无褶皱和弯折。
采用商品化的聚丙烯隔膜(Celgard2500)作为对比例进行性能测定。
实施例2
一种MFI型沸石涂覆锂离子电池隔膜的制备方法，制备方法包括如下步骤：
1)MFI型沸石的制备：制备硅铝复合前驱体为，将去离子水、氢氧化钠、四丁基溴化铵、Al2(SO4)3·18H2O和硅酸四乙酯按质量比为60：0.27：1.77：0.2：6.2的比例配制混合液，搅拌5min，180℃保温12h，得硅铝复合前驱体。
将上述制备的前驱体经离心机用去离子水清洗已制备的前驱体，室温晾干后再550℃下煅烧8h。
2)粘合剂的制备：聚偏氟乙烯粉末、氮氮二甲基甲酰胺和丁酮按质量比为1：30：25的比例配制混合液，搅拌8min后得粘合剂；
3)MFI沸石涂覆悬浊液的制备：将步骤1)的MFI型沸石、步骤2)的粘合剂和丁酮按质量比为3：15：20的比例配制混合液，经超声波分散25min后，搅拌4h，得均匀稳定的MFI型沸石涂覆悬浊液；
4)MFI沸石涂覆的隔膜的制备：用步骤3)MFI沸石涂覆悬浊液浸渗高分子隔膜20s后，冷却380min；重复上述操作100次，得涂层质量均匀的MFI沸石涂覆的隔膜；
5)MFI沸石涂覆的隔膜的处理：90℃下，将步骤4)的MFI沸石涂覆的隔膜烘干15h，且烘干过程中使隔膜平整，无褶皱和弯折。
实施例3
一种MFI型沸石涂覆锂离子电池隔膜的制备方法，制备方法包括如下步骤：
1)MFI型沸石的制备：制备硅铝复合前驱体为，将去离子水、氢氧化钠、 四丁基溴化铵、Al2(SO4)3·18H2O和硅酸四乙酯按质量比为60：0.27：1.77：0.1：6.2的比例配制混合液，搅拌10min，160℃保温10h，得硅铝复合前驱体。
将上述制备的前驱体经离心机用去离子水清洗已制备的前驱体，室温晾干后再550℃下煅烧8h。
2)粘合剂的制备：聚偏氟乙烯粉末、氮氮二甲基甲酰胺和丁酮按质量比为1：25：20的比例配制混合液，搅拌8min后得粘合剂；
3)MFI沸石涂覆悬浊液的制备：将步骤1)的MFI型沸石、步骤2)的粘合剂和丁酮按质量比为10：30：20的比例配制混合液，经超声波分散300min后，搅拌60h，得均匀稳定的MFI型沸石涂覆悬浊液；
4)MFI沸石涂覆的隔膜的制备：用步骤3)MFI沸石涂覆悬浊液浸渗高分子隔膜30s后，冷却260min；重复上述操作40次，得涂层质量均匀的MFI沸石涂覆的隔膜；
5)MFI沸石涂覆的隔膜的处理：50℃下，将步骤4)的MFI沸石涂覆的隔膜烘干20h，且烘干过程中使隔膜平整，无褶皱和弯折。
实施例4
一种MFI型沸石涂覆锂离子电池隔膜的制备方法，制备方法包括如下步骤：
1)MFI型沸石的制备：制备硅铝复合前驱体为，将去离子水、氢氧化钠、四丁基溴化铵、Al2(SO4)3·18H2O和硅酸四乙酯按质量比为60：0.27：1.77：0.05：6.2的比例配制混合液，搅拌14min，170℃保温12h，得硅铝复合前驱体。
将上述制备的前驱体经离心机用去离子水清洗已制备的前驱体，室温晾干后再550℃下煅烧8h。
2)粘合剂的制备：聚偏氟乙烯粉末、氮氮二甲基甲酰胺和丁酮按质量比为1：50：50的比例配制混合液，搅拌10min后得粘合剂；
3)MFI沸石涂覆悬浊液的制备：将步骤1)的MFI型沸石、步骤2)的粘合剂和丁酮按质量比为8：20：40的比例配制混合液，经超声波分散500min后，搅拌3h，得均匀稳定的MFI型沸石涂覆悬浊液；
4)MFI沸石涂覆的隔膜的制备：用步骤3)MFI沸石涂覆悬浊液浸渗高分子隔膜15s后，冷却200min；重复上述操作12次，得涂层质量均匀的MFI沸石涂覆的隔膜；
5)MFI沸石涂覆的隔膜的处理：40℃下，将步骤4)的MFI沸石涂覆的隔膜烘干25h，且烘干过程中使隔膜平整，无褶皱和弯折。
实施例5
一种MFI型沸石涂覆锂离子电池隔膜的制备方法，制备方法包括如下步骤：
1)MFI型沸石的制备：制备纯氧化硅前驱体为，将二氧化硅粉末、氢氧化钠和氢氧化四丙基胺按质量比为100：7：30的比例配制混合液，搅拌15min，120℃保温12h，得纯氧化硅前驱体。
将上述制备的前驱体经离心机用去离子水清洗已制备的前驱体，室温晾干后再550℃下煅烧8h。
2)粘合剂的制备：聚偏氟乙烯粉末、氮氮二甲基甲酰胺和丁酮按质量比为1：20：15的比例配制混合液，搅拌7min后得粘合剂；
3)MFI沸石涂覆悬浊液的制备：将步骤1)的MFI型沸石、步骤2)的粘合剂和丁酮按质量比为4：8：20的比例配制混合液，经超声波分散400min后，搅拌10h，得均匀稳定的MFI型沸石涂覆悬浊液；
4)MFI沸石涂覆的隔膜的制备：用步骤3)MFI沸石涂覆悬浊液浸渗高分 子隔膜20s后，冷却350min；重复上述操作15次，得涂层质量均匀的MFI沸石涂覆的隔膜；
5)MFI沸石涂覆的隔膜的处理：70℃下，将步骤4)的MFI沸石涂覆的隔膜烘干18h，且烘干过程中使隔膜平整，无褶皱和弯折。
上述各实施例所用原料种类比例及其性能测试得到数据如表1所示。
表1
Figure PCTCN2016090620-appb-000001
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均在本发明待批权利要求保护范围之内。

Claims (10)

  1. 一种MFI型沸石涂覆锂离子电池隔膜的制备方法，其特征在于，所述制备方法包括如下步骤：
    1)制备MFI型沸石：制备硅铝复合前驱体或纯氧化硅前驱体，经离心机用去离子水清洗已制备的前驱体，室温晾干后再高温煅烧；
    2)制备粘合剂：将聚偏氟乙烯粉末、氮氮二甲基甲酰胺和丁酮按质量比为1：1～50：1～50的比例配制的混合液搅拌5～10min；
    3)制备MFI沸石涂覆悬浊液：将步骤1)的MFI型沸石、步骤2)的粘合剂和丁酮按质量比为1～10：1～100：1～1000的比例配制的混合液经超声波1～1000min处理后，搅拌1～100h；
    4)制备MFI沸石涂覆的隔膜：将高分子隔膜用步骤3)MFI沸石涂覆悬浊液浸渗5～100s后，冷却1～1000min；重复该操作1～1000次，得涂层质量均匀的MFI沸石涂覆的隔膜；
    5)处理MFI沸石涂覆的隔膜：30～90℃下，将步骤4)的MFI沸石涂覆的隔膜烘干10～100h。
  2. 如权利要求1所述的一种MFI型沸石涂覆锂离子电池隔膜的制备方法，其特征在于，所述步骤1)中制备硅铝复合前驱体包括：将去离子水、氢氧化钠、四丁基溴化铵、Al2(SO4)3·18H2O和硅酸四乙酯按质量比为60：0.27：1.77：0～0.4：6.2的比例配制的混合液搅拌5～20min，160～180℃保温10～12h。
  3. 如权利要求1所述的一种MFI型沸石涂覆锂离子电池隔膜的制备方法，其特征在于，所述步骤1)中制备纯氧化硅前驱体包括：将二氧化硅粉末、氢氧化钠和氢氧化四丙基胺按质量比为90～110：5～10：20～30的比例配制的混合液搅拌5～20min，100～150℃下保温10～15h。
  4. 如权利要求3所述的一种MFI型沸石涂覆锂离子电池隔膜的制备方法，其特征在于，将二氧化硅粉末、氢氧化钠和四丙基氢氧化铵按质量比为100：7：30的比例配制的混合液搅拌10min，120℃下保温12h。
  5. 如权利要求1所述的一种MFI型沸石涂覆锂离子电池隔膜的制备方法，其特征在于，所述步骤1)中所述高温煅烧包括：550℃下煅烧8h。
  6. 如权利要求1所述的一种MFI型沸石涂覆锂离子电池隔膜的制备方法，其特征在于，所述二氧化硅粒径为5nm-1μm。
  7. 如权利要求1所述的一种MFI型沸石涂覆锂离子电池隔膜的制备方法，其特征在于，所述MFI型沸石中硅铝元素含量比例为不小于1:1。
  8. 如权利要求1所述的一种MFI型沸石涂覆锂离子电池隔膜的制备方法，其特征在于，所述MFI型沸石涂覆层厚度为0.1μm-300μm。
  9. 如权利要求1所述的一种MFI型沸石涂覆锂离子电池隔膜的制备方法，其特征在于，所制备的MFI型沸石涂覆的锂离子电池隔膜厚度为10μm-500μm。
  10. 如权利要求1所述的一种MFI型沸石涂覆锂离子电池隔膜的制备方法，其特征在于，所述的高分子隔膜为聚乙烯、聚丙烯或聚酰亚胺。
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CN103107301A (zh) * 2013-01-17 2013-05-15 中国科学院金属研究所 一种新型无机涂层锂离子电池隔膜及其制备方法
CN103400953A (zh) * 2013-07-19 2013-11-20 中国科学院金属研究所 一种具有无机涂层的锌银电池复合隔膜及其制备方法
CN104556135A (zh) * 2015-01-28 2015-04-29 中国石油大学(北京) 一种用于合成zsm-5沸石分子筛的水热合成体系及其应用
CN105140447A (zh) * 2015-07-23 2015-12-09 中国科学院上海硅酸盐研究所 一种锂硫电池用功能性复合隔膜及其制备方法

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DE102018200978A1 (de) * 2018-01-23 2019-07-25 Robert Bosch Gmbh Separator für eine Batteriezelle und Batteriezelle
CN114883748A (zh) * 2022-04-14 2022-08-09 南京航空航天大学 一种用于锂离子电池的复合隔膜及其制备方法
WO2025213294A1 (zh) * 2024-04-07 2025-10-16 深圳市星源材质科技股份有限公司 一种固态电解质及其制备方法和应用

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