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CN107195963A - A kind of polymer dielectric of high conductivity and preparation method thereof - Google Patents

A kind of polymer dielectric of high conductivity and preparation method thereof Download PDF

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CN107195963A
CN107195963A CN201710249328.0A CN201710249328A CN107195963A CN 107195963 A CN107195963 A CN 107195963A CN 201710249328 A CN201710249328 A CN 201710249328A CN 107195963 A CN107195963 A CN 107195963A
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lithium
high conductivity
polymer
polymer dielectric
solution
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白永平
赵彦彪
安茂忠
陈国荣
白杨
李卫东
席丹
殷晓芬
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Wuxi Haite New Material Research Institute Co Ltd
Wuxi Research Institute of New Materials of Harbin Institute of Technology
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Wuxi Haite New Material Research Institute Co Ltd
Wuxi Research Institute of New Materials of Harbin Institute of Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565Polymeric materials, e.g. gel-type or solid-type
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0017Non-aqueous electrolytes
    • H01M2300/0065Solid electrolytes
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    • Y02E60/10Energy storage using batteries

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Abstract

本发明公开了一种高导电率的聚合物电解质及其制备方法,本发明的聚合物电解质由溶解有锂盐的聚碳酸酯与基底聚合物混合而成;其中,溶解有锂盐的聚碳酸酯作为基体,其为导电组分;基底聚合物为支撑体。本发明的聚合物电解质制备简单,室温电导率高。

The invention discloses a high-conductivity polymer electrolyte and a preparation method thereof. The polymer electrolyte of the invention is formed by mixing polycarbonate dissolved with lithium salt and a base polymer; wherein, the polycarbonate dissolved with lithium salt The ester serves as the matrix, which is the conductive component; the base polymer is the support. The polymer electrolyte of the invention is simple to prepare and has high conductivity at room temperature.

Description

一种高导电率的聚合物电解质及其制备方法A kind of polymer electrolyte with high conductivity and preparation method thereof

技术领域technical field

本发明涉及化工生产领域,具体涉及一种高导电率的聚合物电解质及其制备方法。The invention relates to the field of chemical production, in particular to a high-conductivity polymer electrolyte and a preparation method thereof.

背景技术Background technique

目前,全球范围内面临着传统化石能源日趋枯竭的能源危机以及日益严重的环境问题。因此,发展新能源,建立高效、清洁、经济、安全的能源体系迫在眉睫。由于锂电池具有能量密度高、循环寿命长、无记忆效应、可快速充放电等优点,成为不可替代的优良储能设备。锂电池自20世纪90年代初由Sony公司正式商业化以来发展非常迅速,已成为目前在手机、笔记本电脑和数码相机等小型数码电子产品上最常见的主流储能器件。然而,传统锂电池采用的液态电解质,具有易挥发、易燃、易爆等缺点,具有重大安全隐患。随着锂离子电池向大型动力电源应用领域如纯电动汽车、航空航天及大型储能等方面的迅速发展,电池的容量和能量密度不断增大,其电流倍率和功率密度也不断提高,应用可谓越来越广泛,从而使锂电池的安全问题日趋突出。At present, the world is facing an energy crisis of depletion of traditional fossil energy sources and increasingly serious environmental problems. Therefore, it is imminent to develop new energy and establish an efficient, clean, economical and safe energy system. Due to the advantages of high energy density, long cycle life, no memory effect, and fast charging and discharging, lithium batteries have become irreplaceable excellent energy storage devices. Lithium batteries have developed very rapidly since they were officially commercialized by Sony in the early 1990s, and have become the most common mainstream energy storage devices in small digital electronic products such as mobile phones, notebook computers and digital cameras. However, the liquid electrolyte used in traditional lithium batteries has the disadvantages of being volatile, flammable, and explosive, which poses a major safety hazard. With the rapid development of lithium-ion batteries to large-scale power supply applications such as pure electric vehicles, aerospace and large-scale energy storage, the capacity and energy density of batteries continue to increase, and their current rate and power density also continue to increase. The application can be described as More and more widespread, so that the safety of lithium batteries has become increasingly prominent.

另一方面,聚合物电解质电池具有安全性能好、能量密度高、工作温度区间广、循环寿命长等优点而得到了广泛的认可,是锂离子电池领域的研究热点。On the other hand, polymer electrolyte batteries have been widely recognized for their advantages such as good safety performance, high energy density, wide operating temperature range, and long cycle life, and are a research hotspot in the field of lithium-ion batteries.

到目前为止,锂离子电池常用的聚合物电解质主要包括:聚偏氟乙烯-六氟丙烯、聚丙烯腈、聚丙烯酰胺、聚甲基丙烯酸甲酯、聚氧乙烯、聚氧丙烯等。可是这些聚合物都有一定的缺点,例如聚氧乙烯、聚氧丙烯虽然可以用来作为全固态聚合物电解质,然而,低的离子电导率限制了它们的应用。可以说,目前没有电导率、电化学稳定性及界面稳定性等各方面性能均令人满意的聚合物电解质。So far, the commonly used polymer electrolytes for lithium-ion batteries mainly include: polyvinylidene fluoride-hexafluoropropylene, polyacrylonitrile, polyacrylamide, polymethyl methacrylate, polyoxyethylene, polyoxypropylene, etc. However, these polymers have certain disadvantages. For example, although polyoxyethylene and polyoxypropylene can be used as all-solid polymer electrolytes, their low ionic conductivity limits their applications. It can be said that there is currently no polymer electrolyte with satisfactory performance in terms of conductivity, electrochemical stability, and interface stability.

发明内容Contents of the invention

为解决上述现有技术中存在的问题,本发明提供一种高导电率的聚合物电解质及其制备方法,本发明提供的聚合物电解质为固态,在安全性高的同时其导电率高。In order to solve the above-mentioned problems in the prior art, the present invention provides a polymer electrolyte with high conductivity and a preparation method thereof. The polymer electrolyte provided by the present invention is solid and has high conductivity while having high safety.

本发明的高导电率的聚合物电解质,该电解质由溶解有锂盐的聚碳酸酯与基底聚合物混合而成,其中,溶解有锂盐的聚碳酸酯作为基体,其为导电组分;基底聚合物为支撑体。The high-conductivity polymer electrolyte of the present invention is formed by mixing polycarbonate dissolved with lithium salt and a base polymer, wherein the polycarbonate dissolved with lithium salt is used as a matrix, which is a conductive component; the base The polymer is the support.

如上所述的高导电率的聚合物电解质,所述锂盐分散在所述聚碳酸酯基体内,所述基底聚合物与溶解有锂盐的聚碳酸酯的质量比为1:9-9:1,所述聚碳酸酯中锂盐的含量为。所述基底聚合物与溶解有锂盐的聚碳酸酯的质量比尤其优选1:9-1:1;所述基底聚合物与溶解有锂盐的聚碳酸酯的质量比特别优选1:9-1:5,所述基底聚合物与溶解有锂盐的聚碳酸酯的质量比更为优选1:9-1:4。The above-mentioned high-conductivity polymer electrolyte, the lithium salt is dispersed in the polycarbonate matrix, and the mass ratio of the base polymer to the polycarbonate dissolved with lithium salt is 1:9-9: 1, the content of lithium salt in the polycarbonate is . The mass ratio of the base polymer to the polycarbonate dissolved with lithium salt is particularly preferably 1:9-1:1; the mass ratio of the base polymer to the polycarbonate dissolved with lithium salt is particularly preferably 1:9-1:1 1:5, the mass ratio of the base polymer to the polycarbonate dissolved in lithium salt is more preferably 1:9-1:4.

根据如上所述的高导电率的聚合物电解质,所述聚碳酸酯为聚碳酸乙烯酯、聚碳酸丙烯酯或聚碳酸亚乙烯酯中的一种或几种。According to the high-conductivity polymer electrolyte described above, the polycarbonate is one or more of polyethylene carbonate, polypropylene carbonate or polyvinylene carbonate.

根据如上所述的高导电率的聚合物电解质,所述锂盐为高氯酸锂、六氟磷酸锂、二草酸硼酸锂、六氟砷酸锂、四氟硼酸锂、三氟甲基磺酸锂、双三氟甲基磺酰亚胺锂或双氟磺酰亚胺锂中的一种或几种。According to the polymer electrolyte with high conductivity as described above, the lithium salt is lithium perchlorate, lithium hexafluorophosphate, lithium dioxalate borate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, bis One or more of lithium trifluoromethanesulfonyl imide or lithium bisfluorosulfonyl imide.

根据如上所述的高导电率的聚合物电解质,所述基底聚合物为聚甲基丙烯酸甲酯、聚氧化乙烯、聚偏氟乙烯、聚(偏氟乙烯-六氟丙烯)、、聚丙烯腈、聚乙烯醇中的一种或几种。According to the polymer electrolyte with high conductivity as described above, the base polymer is polymethyl methacrylate, polyethylene oxide, polyvinylidene fluoride, poly(vinylidene fluoride-hexafluoropropylene), polyacrylonitrile , one or more of polyvinyl alcohol.

根据如上所述的高导电率的聚合物电解质,所述聚合物电解质还含有1-50wt%的无机填料和/或快离子导体。According to the polymer electrolyte with high conductivity as described above, the polymer electrolyte further contains 1-50 wt% of inorganic filler and/or fast ion conductor.

根据如上所述的高导电率的聚合物电解质,所述无机填料为二氧化硅、二氧化钛、三氧化二铝、氧化锆、氧化镍、氮化硅、氢氧化镁、硅藻土、蒙脱土和高岭土中一种或几种;所述快离子导体为Li7La3Zr2O12、Li10GeP2S12、Li3OCl0.5Br0.5、Li3xLa(2/3)-xTiO3、Li5La3Ta2O12、Li5La3Nb2O12、Li5 .5La3Nb1 .75In0.25O12、Li3N-LiCl、Li3N-LiBr、Li3N-LiI、Li14Zn( GeO4 )4、LiZr2( PO4 )3、Li3OCl、LiPON和Li2S-MaSb中的一种或几种,其中,0 .04<x<0 .14,M=Al、Si或P,a和b的取值分别为1-3。According to the polymer electrolyte with high conductivity as described above, the inorganic filler is silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, nickel oxide, silicon nitride, magnesium hydroxide, diatomaceous earth, montmorillonite and one or more of kaolin; the fast ion conductors are Li 7 La 3 Zr 2 O 12 , Li 10 GeP 2 S 12 , Li 3 OCl 0.5 Br 0.5 , Li 3x La (2/3)-x TiO 3 , Li 5 La 3 Ta 2 O 12 , Li 5 La 3 Nb 2 O 12 , Li 5 .5 La 3 Nb 1 .75 In 0.25 O 12 , Li 3 N-LiCl, Li 3 N-LiBr, Li 3 N- One or more of LiI, Li 14 Zn(GeO 4 ) 4 , LiZr 2 (PO 4 ) 3 , Li 3 OCl, LiPON and Li 2 S-MaSb, where 0.04<x<0.14, M=Al, Si or P, and the values of a and b are 1-3 respectively.

根据如上所述的高导电率的聚合物电解质的制备方法,其包括下述步骤:According to the preparation method of the polymer electrolyte with high conductivity as described above, it comprises the following steps:

(1)先将聚碳酸酯溶解于溶剂中,得到聚碳酯溶液;(1) First dissolve polycarbonate in a solvent to obtain a polycarbonate solution;

(2)将锂盐加入聚碳酯溶液中,搅拌至完全溶解;(2) Add the lithium salt into the polycarbonate solution and stir until completely dissolved;

(3)将基底聚合物加入溶液,搅拌至完全溶解,干燥后得到聚合物电解质。(3) Add the base polymer into the solution, stir until completely dissolved, and obtain a polymer electrolyte after drying.

根据如上所述的制备方法,其在步骤3) 中,将无机填料和/或快离子导体与基底聚合物同时加入溶液,混匀得均一的溶液。According to the above-mentioned preparation method, in step 3), the inorganic filler and/or fast ion conductor and the base polymer are added to the solution at the same time, and mixed to obtain a uniform solution.

根据如上所述的制备方法,所述溶剂为乙腈、二甲基亚砜、环丁砜、亚硫酸二甲酯、亚硫酸二乙酯、丙酮、四氢呋喃、三氯甲烷、乙酸乙酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮中的一种或几种。According to the above-mentioned preparation method, the solvent is acetonitrile, dimethyl sulfoxide, sulfolane, dimethyl sulfite, diethyl sulfite, acetone, tetrahydrofuran, chloroform, ethyl acetate, N,N- One or more of dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

图1是本发明的固态聚合物电解质的内部结构示意图。如图1所示,本发明的聚合物电解质,其整体是固态的,聚碳酸酯为基体,基底聚合物为支撑体,基底聚合物分散在聚碳酸酯中,锂离子以及与锂离子构成锂盐的阴离子也随机分散,锂离子进行导电。Fig. 1 is a schematic diagram of the internal structure of the solid polymer electrolyte of the present invention. As shown in Figure 1, the polymer electrolyte of the present invention is solid as a whole, polycarbonate is the matrix, the base polymer is the support, the base polymer is dispersed in the polycarbonate, lithium ions and lithium ions form lithium Anions of the salt are also randomly dispersed, and lithium ions conduct electricity.

本发明的聚合物电解质制备方法简单,室温电导率高、电化学和界面稳定性好。The preparation method of the polymer electrolyte of the invention is simple, the room temperature conductivity is high, and the electrochemical and interface stability are good.

附图说明Description of drawings

图1是本发明的固态聚合物电解质的内部结构示意图。Fig. 1 is a schematic diagram of the internal structure of the solid polymer electrolyte of the present invention.

图2是实施例1中制得的固态聚合物电解质膜的氧化分解电位图。FIG. 2 is an oxidation decomposition potential diagram of the solid polymer electrolyte membrane prepared in Example 1. FIG.

图3是实施例1中制得的固态聚合物电解质膜的阻抗测试图。FIG. 3 is an impedance test diagram of the solid polymer electrolyte membrane prepared in Example 1. FIG.

具体实施方式detailed description

以下对本发明的优选实施例进行说明,应当理解,此处所描述的优选实施例仅用于说明和解释本发明,并不用于限定本发明。Preferred embodiments of the present invention are described below, and it should be understood that the preferred embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

实施例1Example 1

将2.7g 聚碳酸乙烯酯和100g N-甲基吡咯烷酮加入250 ml试剂瓶室温搅拌6 h获得均匀溶液,将1.8g 双三氟甲基磺酰亚胺锂加入到上述溶液当中,在常温下搅拌6 h,待完全溶解后加入0.5g聚偏氟乙烯,搅拌得到均匀的混合溶液,将该混合溶液注入聚四氟乙烯(PTFE)模具中晾干成膜,真空干燥即得到固态聚合物电解质膜。Add 2.7g polyvinyl carbonate and 100g N-methylpyrrolidone into a 250 ml reagent bottle and stir at room temperature for 6 h to obtain a uniform solution, add 1.8g lithium bistrifluoromethanesulfonimide to the above solution, and stir at room temperature After 6 h, add 0.5g of polyvinylidene fluoride after complete dissolution, stir to obtain a uniform mixed solution, inject the mixed solution into a polytetrafluoroethylene (PTFE) mold to dry to form a film, and vacuum dry to obtain a solid polymer electrolyte membrane .

实施例2Example 2

将0. 5 g 聚碳酸乙烯酯和100g亚硫酸二甲酯加入250 ml试剂瓶室温搅拌6 h获得均匀溶液,将4.5g双氟磺酰亚胺锂加入到上述溶液当中,在常温下搅拌6 h,待完全溶解后加入1.25g聚(偏氟乙烯-六氟丙烯),搅拌得到均匀的混合溶液,将该混合溶液注入聚四氟乙烯(PTFE)模具中晾干成膜,真空干燥即得到固态聚合物电解质膜。Add 0.5 g of polyvinyl carbonate and 100 g of dimethyl sulfite to a 250 ml reagent bottle and stir at room temperature for 6 h to obtain a uniform solution. Add 4.5 g of lithium bisfluorosulfonyl imide to the above solution and stir at room temperature for 6 h. h, after complete dissolution, add 1.25g poly(vinylidene fluoride-hexafluoropropylene), stir to obtain a uniform mixed solution, pour the mixed solution into a polytetrafluoroethylene (PTFE) mold to dry to form a film, and vacuum dry to obtain Solid polymer electrolyte membrane.

实施例3Example 3

将3g 聚碳酸丙烯酯和100 g 乙腈加入100 ml试剂瓶室温搅拌6 h获得均匀溶液,将3g高氯酸锂加入到上述溶液当中,在常温下搅拌6 h,待完全溶解后加入6g 聚乙烯醇,搅拌得到均匀的混合溶液,将该混合溶液注入聚四氟乙烯(PTFE)模具中晾干成膜,真空干燥即得到固态聚合物电解质膜。Add 3g of polypropylene carbonate and 100g of acetonitrile into a 100ml reagent bottle and stir at room temperature for 6 hours to obtain a homogeneous solution. Add 3g of lithium perchlorate to the above solution and stir for 6 hours at room temperature. After completely dissolving, add 6g of polyethylene Alcohol, stirring to obtain a uniform mixed solution, injecting the mixed solution into a polytetrafluoroethylene (PTFE) mold to dry to form a film, and vacuum drying to obtain a solid polymer electrolyte membrane.

实施例4Example 4

将0.9 g 聚碳酸亚乙烯酯和100g四氢呋喃加入250 ml试剂瓶室温搅拌6 h获得均匀溶液,将3.6g三氟甲基磺酸锂加入到上述溶液当中,在常温下搅拌6 h,待完全溶解后加入0.56聚丙烯腈,充分溶解后,加入2.5g纳米二氧化硅颗粒,搅拌得到均匀的混合溶液,将该混合溶液注入聚四氟乙烯(PTFE)模具中晾干成膜,真空干燥即得到固态聚合物电解质膜。Add 0.9 g of polyvinylene carbonate and 100 g of tetrahydrofuran into a 250 ml reagent bottle and stir at room temperature for 6 h to obtain a homogeneous solution. Add 3.6 g of lithium trifluoromethanesulfonate to the above solution, stir at room temperature for 6 h, and wait for complete dissolution Finally, add 0.56 polyacrylonitrile, after fully dissolving, add 2.5g of nano-silica particles, stir to obtain a uniform mixed solution, inject the mixed solution into a polytetrafluoroethylene (PTFE) mold to dry to form a film, and vacuum dry to obtain Solid polymer electrolyte membrane.

实施例5Example 5

将0.9 g 聚碳酸亚乙烯酯和100g三氯甲烷加入250 ml试剂瓶室温搅拌6 h获得均匀溶液,将2.1g四氟硼酸锂加入到上述溶液当中,在常温下搅拌6 h,待完全溶解后加入27g聚甲基丙烯酸甲酯,充分溶解后,加入3g Li5La3Ta2O12,搅拌得到均匀的混合溶液,将该混合溶液注入聚四氟乙烯(PTFE)模具中晾干成膜,真空干燥即得到固态聚合物电解质膜。Add 0.9 g of polyvinylene carbonate and 100 g of chloroform to a 250 ml reagent bottle and stir at room temperature for 6 h to obtain a uniform solution. Add 2.1 g of lithium tetrafluoroborate to the above solution and stir at room temperature for 6 h. After completely dissolving Add 27g polymethyl methacrylate, fully dissolve, add 3g Li 5 La 3 Ta 2 O 12 , stir to obtain a uniform mixed solution, inject the mixed solution into a polytetrafluoroethylene (PTFE) mold and dry it to form a film. The solid polymer electrolyte membrane is obtained by vacuum drying.

实施例6Example 6

将0.3g 聚碳酸丙烯酯和100 g 乙腈加入100 ml试剂瓶室温搅拌6 h获得均匀溶液,将0.3g 高氯酸锂加入到上述溶液当中,在常温下搅拌6 h,待完全溶解后加入4.2g 聚乙烯醇,搅拌得到均匀的混合溶液,将该混合溶液注入聚四氟乙烯(PTFE)模具中晾干成膜,真空干燥即得到固态聚合物电解质膜。Add 0.3g of polypropylene carbonate and 100g of acetonitrile into a 100ml reagent bottle and stir at room temperature for 6 hours to obtain a uniform solution. Add 0.3g of lithium perchlorate to the above solution and stir for 6 hours at room temperature. After it is completely dissolved, add 4.2 g polyvinyl alcohol, stir to obtain a uniform mixed solution, pour the mixed solution into a polytetrafluoroethylene (PTFE) mold to dry to form a film, and vacuum dry to obtain a solid polymer electrolyte membrane.

实施例7Example 7

将3.6g 聚碳酸丙烯酯和100 g 乙腈加入100 ml试剂瓶室温搅拌6 h获得均匀溶液,将0.9g 高氯酸锂加入到上述溶液当中,在常温下搅拌6 h,待完全溶解后加入13.5g 聚乙烯醇,搅拌得到均匀的混合溶液,将该混合溶液注入聚四氟乙烯(PTFE)模具中晾干成膜,真空干燥即得到固态聚合物电解质膜。Add 3.6g of polypropylene carbonate and 100g of acetonitrile into a 100ml reagent bottle and stir at room temperature for 6 hours to obtain a homogeneous solution. Add 0.9g of lithium perchlorate to the above solution and stir for 6 hours at room temperature. After it is completely dissolved, add 13.5 g polyvinyl alcohol, stir to obtain a uniform mixed solution, pour the mixed solution into a polytetrafluoroethylene (PTFE) mold to dry to form a film, and vacuum dry to obtain a solid polymer electrolyte membrane.

对比例1Comparative example 1

将聚氧化乙烯10g、高氯酸锂2g,溶剂乙腈200g混合均匀后,浇注到模具中晾干成膜,真空干燥即得到固体聚合物电解质膜。Mix 10 g of polyethylene oxide, 2 g of lithium perchlorate, and 200 g of solvent acetonitrile evenly, pour into a mold to dry to form a film, and vacuum dry to obtain a solid polymer electrolyte membrane.

对实施例1-7及对比例1中制得的固体聚合物电解质膜测定离子电导率,离子电导率测试的具体方法为:采用电化学工作站,通过测定不锈钢/电解质/不锈钢阻塞电池的交流阻抗来计算得到聚合物电解质离子电导率。具体测试步骤是:在充满氩气的手套箱内,将电解质膜夹在两个不锈钢片之间,组装成阻塞电池,启动软件,设置频率范围为1 Hz~10MHz,振幅为10 mV,可设定需要的温度参数来测试当前电池的交流阻抗。实验结果得到一条直线,直线与实轴相交的交点数值即为电解质的本体电阻,记为Rm。电解质的离子电导率的计算公式: 。式中:σ为离子电导率,L 为电解质的厚度;S 为隔膜与电极接触的面积;Rm 为本体电阻。The ionic conductivity of the solid polymer electrolyte membrane prepared in Examples 1-7 and Comparative Example 1 is measured. The specific method of the ionic conductivity test is: using an electrochemical workstation, by measuring the AC impedance of the stainless steel/electrolyte/stainless steel blocking battery To calculate the ionic conductivity of the polymer electrolyte. The specific test steps are: in a glove box filled with argon, sandwich the electrolyte membrane between two stainless steel sheets, assemble it into a blocking cell, start the software, set the frequency range from 1 Hz to 10 MHz, and the amplitude to 10 mV. Set the required temperature parameters to test the AC impedance of the current battery. A straight line is obtained from the experimental results, and the value of the intersection point where the line intersects the real axis is the bulk resistance of the electrolyte, which is denoted as Rm. The formula for calculating the ionic conductivity of an electrolyte is: . In the formula: σ is the ionic conductivity, L is the thickness of the electrolyte; S is the contact area between the separator and the electrode; Rm is the bulk resistance.

表1Table 1

由表1可知,本发明制得的聚合物电解质其室温电导率尤其优异。另外,图1是实施例1中制得的固态聚合物电解质膜的氧化分解电位图。图2是实施例1中制得的固态聚合物电解质膜的阻抗测试图。由图1可知,氧化分解电位>4.5V,制得的固态聚合物电解质膜电化学稳定性好。由图2可知,稳定后阻抗增大不明显,制得的固态聚合物电解质膜表明界面稳定性好。It can be seen from Table 1 that the room temperature conductivity of the polymer electrolyte prepared by the present invention is particularly excellent. In addition, FIG. 1 is an oxidative decomposition potential diagram of the solid polymer electrolyte membrane prepared in Example 1. FIG. 2 is an impedance test diagram of the solid polymer electrolyte membrane prepared in Example 1. FIG. It can be seen from Figure 1 that the oxidation decomposition potential is >4.5V, and the prepared solid polymer electrolyte membrane has good electrochemical stability. It can be seen from Figure 2 that the impedance does not increase significantly after stabilization, and the prepared solid polymer electrolyte membrane shows good interface stability.

Claims (10)

1. a kind of polymer dielectric of high conductivity, it is characterised in that the electrolyte by be dissolved with the makrolon of lithium salts with Substrate polymer is mixed;Wherein, the makrolon of lithium salts is dissolved with as matrix, and it is conductive component;Substrate polymer For supporter.
2. the polymer dielectric of high conductivity according to claim 1, it is characterised in that the lithium salts is dispersed in described In polycarbonate matrix, the mass ratio of makrolon of the substrate polymer with being dissolved with lithium salts is 1:9-9:1, the poly- carbon The content of lithium salts is 40-90wt% in acid esters.
3. the polymer dielectric of high conductivity according to claim 2, it is characterised in that the substrate polymer with it is molten The mass ratio that solution has the makrolon of lithium salts is 1:9-1:1.
4. the polymer dielectric of high conductivity according to claim 1 or 2, it is characterised in that the makrolon is One or more in poly- ethylene carbonate, polypropylene carbonate or polymerized thylene carbonate vinyl acetate;The lithium salts is lithium perchlorate, six Lithium fluophosphate, dioxalic acid lithium borate, hexafluoroarsenate lithium, LiBF4, trifluoromethyl sulfonic acid lithium, bis trifluoromethyl sulfimide One or more in lithium or double fluorine sulfimide lithiums.
5. the polymer dielectric of high conductivity according to claim 1 or 2, it is characterised in that the substrate polymer For polymethyl methacrylate, polyethylene glycol oxide, Kynoar, poly- (biasfluoroethylene-hexafluoropropylene), polyacrylonitrile, poly- second One or more in enol.
6. the polymer dielectric of high conductivity according to claim 1, it is characterised in that the polymer dielectric is also Inorganic filler and/or fast-ionic conductor containing 1~50wt%.
7. the polymer dielectric of high conductivity according to claim 6, it is characterised in that the inorganic filler is dioxy SiClx, titanium dioxide, alundum (Al2O3), zirconium oxide, nickel oxide, silicon nitride, magnesium hydroxide, diatomite, montmorillonite and kaolin Middle one or more;The fast-ionic conductor is Li7La3Zr2O12、Li10GeP2S12、Li3OCl0.5Br0.5、Li5La3Ta2O12、Li5La3Nb2O12、Li5 .5La3Nb1 .75In0.25O12、Li3N-LiCl、 、Li3N-LiI、Li14Zn( GeO4 )4、LiZr2( PO4 )3、Li3OCl, LiPON and Li2One or more in S-MaSb, its In, 0 .04<x<0 .14, M=Al, Si or P, a and b value are respectively 1-3.
8. the method for preparing polymer electrolytes of the high conductivity according to claim 1-7, it is characterised in that including under State step:
(1)First makrolon is dissolved in solvent, poly- carbon ester solution is obtained;
(2)Lithium salts is added in poly- carbon ester solution, stirring is to being completely dissolved;
(3)Substrate polymer is added into solution, stirring obtains polymer dielectric to being completely dissolved after drying.
9. preparation method according to claim 8, it is characterised in that in step 3) in, by inorganic filler and/or it is fast from Sub- conductor adds solution simultaneously with substrate polymer, the solution for mixing homogeneous.
10. preparation method according to claim 8 or claim 9, it is characterised in that the solvent is acetonitrile, dimethyl sulfoxide (DMSO), ring Fourth sulfone, dimethyl sulfite, sulfurous acid diethyl ester, acetone, tetrahydrofuran, chloroform, ethyl acetate, N, N- dimethyl formyls One or more in amine, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE.
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Application publication date: 20170922