CN114613615A - Ultrathin polyoxyethylene-based solid electrolyte film and preparation method thereof - Google Patents

Ultrathin polyoxyethylene-based solid electrolyte film and preparation method thereof Download PDF

Info

Publication number
CN114613615A
CN114613615A CN202210372914.5A CN202210372914A CN114613615A CN 114613615 A CN114613615 A CN 114613615A CN 202210372914 A CN202210372914 A CN 202210372914A CN 114613615 A CN114613615 A CN 114613615A
Authority
CN
China
Prior art keywords
solid electrolyte
polyoxyethylene
hydrogen bond
polyethylene oxide
ultra
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210372914.5A
Other languages
Chinese (zh)
Other versions
CN114613615B (en
Inventor
王静毅
王补欢
臧孝贤
张继国
马福元
马紫峰
陈章伟
傅维栋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Zheneng Beilun Power Generation Co ltd
Zhejiang Energy Group Research Institute Co Ltd
Original Assignee
Zhejiang Zheneng Beilun Power Generation Co ltd
Zhejiang Energy Group Research Institute Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Zheneng Beilun Power Generation Co ltd, Zhejiang Energy Group Research Institute Co Ltd filed Critical Zhejiang Zheneng Beilun Power Generation Co ltd
Priority to CN202210372914.5A priority Critical patent/CN114613615B/en
Publication of CN114613615A publication Critical patent/CN114613615A/en
Application granted granted Critical
Publication of CN114613615B publication Critical patent/CN114613615B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54Electrolytes
    • H01G11/56Solid electrolytes, e.g. gels; Additives therein
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Conductive Materials (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The invention relates to a preparation method of an ultrathin polyoxyethylene-based solid electrolyte film, which comprises the following steps: dispersing polyoxyethylene and electrolyte salt into acetonitrile according to a set molar ratio, and stirring until the polyoxyethylene and the electrolyte salt are completely dissolved; adding a cross-linking agent and polyoxyethylene into the solution according to a set molar ratio of a hydrogen bond acceptor, and stirring until the cross-linking agent and the polyoxyethylene are completely dispersed to obtain a dispersion liquid; and dripping the obtained dispersion liquid on two sides of the polymer support substrate respectively, uniformly coating the dispersion liquid, drying to remove the solvent, and obtaining the film on two sides of the polymer support substrate. The invention has the beneficial effects that: the invention can realize the precise regulation and control of the mechanical property and the thickness of the solid electrolyte film by controlling the molar ratio of the cross-linking agent to the polyethylene oxide and the rolling distance. For the design difficulty of the ultrathin solid electrolyte film, the invention provides a feasible design idea, has the advantages of simplicity, economy and the like, and can be used for super capacitors and batteries to improve the safety of devices.

Description

一种超薄聚氧化乙烯基固态电解质薄膜及其制备方法A kind of ultra-thin polyoxyethylene solid electrolyte film and preparation method thereof

技术领域technical field

本发明属于固态电解质技术领域,尤其涉及一种超薄聚氧化乙烯基固态电解质薄膜及其制备方法。The invention belongs to the technical field of solid electrolytes, and in particular relates to an ultra-thin polyoxyethylene solid electrolyte film and a preparation method thereof.

背景技术Background technique

固态电解质又称为快离子导体,按固态电解质的组分可大致分为无机物固态电解质、聚合物固态电解质和复合物固态电解质。聚合物固态电解质是由极性高分子和金属盐络合而成,与有机液态电解质组分相似。与有机液态电解质相比,聚合物固态电解质具有优良的安全性、优异的热稳定性、较宽的电化学窗口(略高于有机液态电解质)、良好的灵活性和可加工性等优点。Solid electrolytes, also known as fast ion conductors, can be roughly divided into inorganic solid electrolytes, polymer solid electrolytes and composite solid electrolytes according to the components of solid electrolytes. Polymer solid electrolytes are composed of polar polymers and metal salts complexed, similar to organic liquid electrolytes. Compared with organic liquid electrolytes, polymer solid electrolytes have the advantages of superior safety, excellent thermal stability, wider electrochemical window (slightly higher than that of organic liquid electrolytes), good flexibility, and processability.

当前针对全固态聚合物电解质的研究大多数都集中在增强离子电导率和改善界面稳定性上,电解质膜的厚度受到的关注较少。黄云辉等人的论文:Most of the current research on all-solid-state polymer electrolytes focuses on enhancing ionic conductivity and improving interfacial stability, and the thickness of electrolyte membranes has received less attention. The paper by Yunhui Huang et al:

Jingyi Wu,Lixia Yuan,Wuxing Zhang,Zhen Li,Xiaolin Xie and YunhuiHuang,“Reducing the thickness of solid-state electrolyte membranes for high-energy lithium batteries”.Energy Environ.Sci.,2021,14,12-36.Jingyi Wu, Lixia Yuan, Wuxing Zhang, Zhen Li, Xiaolin Xie and Yunhui Huang, “Reducing the thickness of solid-state electrolyte membranes for high-energy lithium batteries”. Energy Environ. Sci., 2021, 14, 12-36.

论文中指出,电池内阻取决于固态电解质的离子电导和电荷转移阻抗,其中离子电导(G=σA/L,G为离子电导、σ为离子电导率、A为面积、L为厚度)反比于电解质厚度,主要原因是降低厚度缩短了离子在电解质中的传输时间。因此,制备超薄固态电解质薄膜,可提高其离子电导。It is pointed out in the paper that the internal resistance of the battery depends on the ionic conductance and charge transfer resistance of the solid electrolyte, where the ionic conductance (G=σA/L, G is the ionic conductivity, σ is the ionic conductivity, A is the area, and L is the thickness) inversely proportional to Electrolyte thickness, the main reason is that reducing the thickness shortens the transport time of ions in the electrolyte. Therefore, the preparation of ultrathin solid electrolyte films can improve their ionic conductivity.

超薄固态电解质薄膜设计的难点在于最小化厚度和维持机械强度之间的矛盾。The difficulty in designing ultrathin solid electrolyte membranes lies in the conflict between minimizing thickness and maintaining mechanical strength.

发明内容SUMMARY OF THE INVENTION

本发明的目的是克服现有技术中的不足,提供一种超薄聚氧化乙烯基固态电解质薄膜及其制备方法。The purpose of the present invention is to overcome the deficiencies in the prior art, and provide an ultra-thin polyoxyethylene vinyl solid electrolyte film and a preparation method thereof.

这种超薄聚氧化乙烯基固态电解质薄膜,包括:聚合物支撑基底和交联修饰的聚氧化乙烯基固态电解质基质,聚合物支撑基底位于两层交联修饰的聚氧化乙烯基固态电解质基质之间;聚合物支撑基底为聚合物薄膜,聚氧化乙烯基固态电解质基质的交联修饰方式为氢键交联。The ultra-thin polyoxyethylene solid electrolyte film includes: a polymer support substrate and a cross-linked modified polyethylene oxide solid electrolyte matrix, and the polymer support substrate is located between two layers of the crosslinked modified polyethylene oxide solid electrolyte substrate The polymer supporting substrate is a polymer film, and the crosslinking modification mode of the polyoxyethylene solid electrolyte matrix is hydrogen bond crosslinking.

作为优选,聚合物支撑基底为绝缘多孔材料,厚度为5~10μm,聚氧化乙烯基固态电解质基质2的厚度为5~15μm。Preferably, the polymer support substrate is an insulating porous material with a thickness of 5-10 μm, and the polyoxyethylene-based solid electrolyte matrix 2 has a thickness of 5-15 μm.

作为优选,聚合物支撑基底材质为聚四氟乙烯、聚偏氟乙烯和聚酰亚胺中的至少一种。Preferably, the material of the polymer support base is at least one of polytetrafluoroethylene, polyvinylidene fluoride and polyimide.

作为优选,超薄聚氧化乙烯基固态电解质薄膜的整体厚度为5~30μm。Preferably, the overall thickness of the ultra-thin polyoxyethylene solid electrolyte film is 5-30 μm.

作为优选,交联修饰的聚氧化乙烯基固态电解质基质为聚氧化乙烯和电解质盐络合形成的固态电解质基质。Preferably, the cross-linked modified polyethylene oxide solid electrolyte matrix is a solid electrolyte matrix formed by the complexation of polyethylene oxide and an electrolyte salt.

作为优选,聚氧化乙烯基固态电解质基质中交联剂氢键供体与聚氧化乙烯氢键受体的摩尔比为1:1~1:10。Preferably, the molar ratio of the hydrogen bond donor of the crosslinking agent to the hydrogen bond acceptor of the polyethylene oxide in the polyethylene oxide solid electrolyte matrix is 1:1 to 1:10.

这种超薄聚氧化乙烯基固态电解质薄膜的制备方法,包括以下步骤:The preparation method of this ultra-thin polyethylene oxide solid electrolyte film comprises the following steps:

步骤1、将聚氧化乙烯和电解质盐按照设定摩尔比分散到乙腈中,搅拌至完全溶解;Step 1. Disperse polyethylene oxide and electrolyte salt into acetonitrile according to the set molar ratio, and stir until completely dissolved;

步骤2、将交联剂和聚氧化乙烯按照设定氢键受体的摩尔比添加到步骤1所得溶液中,搅拌至完全分散,得到分散液;Step 2, adding the crosslinking agent and polyethylene oxide to the solution obtained in step 1 according to the molar ratio of the set hydrogen bond acceptor, and stirring until completely dispersed to obtain a dispersion;

步骤3、将步骤2所得分散液分别滴于聚合物支撑基底两侧,将分散液涂布均匀,烘干去除溶剂,在聚合物支撑基底两侧得到薄膜;Step 3, drop the dispersion obtained in step 2 on both sides of the polymer support substrate respectively, coat the dispersion evenly, dry to remove the solvent, and obtain a film on both sides of the polymer support substrate;

步骤4、将步骤3得到的薄膜-聚合物支撑基底-薄膜结构置于辊压机中,在从大到小的辊压间隙下多次辊压,获得厚度均匀的超薄聚氧化乙烯基固态电解质薄膜,超薄聚氧化乙烯基固态电解质薄膜的聚合物支撑基底孔隙中充满聚氧化乙烯基固态电解质;符号-表示复合连接。Step 4. Place the film-polymer support substrate-film structure obtained in step 3 in a roller press, and roll multiple times under the rolling gap from large to small to obtain an ultra-thin polyoxyethylene solid state with uniform thickness. Electrolyte film, the polymer support base of the ultra-thin polyoxyethylene solid electrolyte film is filled with polyoxyethylene solid electrolyte in the pores; the symbol - represents the composite connection.

作为优选,步骤2中交联剂提供至少两个氢键供体,氢键供体同时与多个聚氧化乙烯链发生氢键交联;具体氢键交联方式为:交联剂提供的氢键供体与聚氧化乙烯中醚氧形成氢键,形成网络化结构,从而提高固态电解质薄膜的机械性能;交联剂包括尿素、硫脲和三羟甲基酚。Preferably, in step 2, the crosslinking agent provides at least two hydrogen bond donors, and the hydrogen bond donors simultaneously undergo hydrogen bond crosslinking with multiple polyethylene oxide chains; the specific hydrogen bond crosslinking method is: the hydrogen bond provided by the crosslinking agent. The bond donor forms a hydrogen bond with the ether oxygen in the polyethylene oxide to form a network structure, thereby improving the mechanical properties of the solid electrolyte film; the cross-linking agent includes urea, thiourea and trimethylolphenol.

作为优选,步骤1中聚氧化乙烯和电解质盐的摩尔比为1:8~1:20;步骤2中交联剂和聚氧化乙烯中氢键受体的摩尔比为1:1~1:10;步骤3中将分散液涂布均匀后,在60℃下烘干12h去除溶剂。Preferably, in step 1, the molar ratio of polyethylene oxide and electrolyte salt is 1:8 to 1:20; in step 2, the molar ratio of crosslinking agent to hydrogen bond acceptor in polyethylene oxide is 1:1 to 1:10. ; In step 3, after the dispersion is evenly coated, the solvent is removed by drying at 60° C. for 12 hours.

作为优选,步骤3中将分散液涂布在聚合物支撑基底两侧时的涂布高度为100~500μm。Preferably, in step 3, the coating height when the dispersion liquid is coated on both sides of the polymer support substrate is 100-500 μm.

本发明的有益效果是:The beneficial effects of the present invention are:

本发明提出的固态电解质薄膜为由聚合物支撑基底和交联修饰的聚氧化乙烯基固态电解质构成的薄膜,是经多次辊压后获得的5~30μm的均匀固态电解质薄膜;聚合物支撑基底为聚合物薄膜,交联修饰为氢键交联。The solid electrolyte film proposed by the present invention is a film composed of a polymer support substrate and a cross-linked modified polyoxyethylene solid electrolyte, and is a uniform solid electrolyte film of 5-30 μm obtained after rolling for many times; the polymer support substrate For polymer films, the crosslinking modification is hydrogen bond crosslinking.

绝缘多孔的聚合物支撑基底不仅作为固态电解质薄膜的支撑骨架,同时保证离子传输和电子绝缘。聚氧化乙烯含有醚氧非共用电子对,对氢键有很强的亲合力;本发明选用多氢键供体的交联剂,交联剂的多个氢供体同时与不同的聚氧化乙烯链形成氢键,不同的聚氧化乙烯链通过交联剂相互连接,实现网络化结构,从而提高固态电解质的机械性能;本发明通过对固态电解质薄膜的多次辊压,可降低因辊压造成的薄膜变形,获得5~30μm的均匀固态电解质薄膜。The insulating porous polymer support substrate not only serves as the support skeleton of the solid electrolyte film, but also ensures ion transport and electronic insulation. Polyoxyethylene contains ether-oxygen non-shared electron pairs, and has a strong affinity for hydrogen bonds; the present invention selects a cross-linking agent of multiple hydrogen bond donors, and multiple hydrogen donors of the cross-linking agent are simultaneously combined with different polyethylene oxides. The chains form hydrogen bonds, and different polyethylene oxide chains are connected to each other through a cross-linking agent to achieve a networked structure, thereby improving the mechanical properties of the solid electrolyte; the present invention can reduce the damage caused by rolling by rolling the solid electrolyte film for many times. The thin film was deformed to obtain a uniform solid electrolyte film of 5-30 μm.

本发明通过对交联剂/聚氧化乙烯的摩尔比和辊压间距的控制,可实现固态电解质薄膜的机械性能和厚度的精确调控。对于超薄固态电解质薄膜设计难点,本发明提供一种可行性的设计思路,并且具有简单经济等优点,可用于超级电容器、电池,以提高器件的安全性。By controlling the molar ratio of the crosslinking agent/polyethylene oxide and the rolling distance, the present invention can realize precise regulation of the mechanical properties and thickness of the solid electrolyte film. For the design difficulties of ultra-thin solid electrolyte films, the present invention provides a feasible design idea, and has the advantages of simplicity and economy, and can be used in supercapacitors and batteries to improve the safety of devices.

附图说明Description of drawings

图1为超薄聚氧化乙烯基固态电解质薄膜的结构示意图;Fig. 1 is a structural schematic diagram of an ultra-thin polyethylene oxide solid electrolyte film;

图2为超薄聚氧化乙烯基固态电解质薄膜的台阶仪扫描图;Fig. 2 is the step meter scanning diagram of ultra-thin polyethylene oxide vinyl solid electrolyte film;

图3为基于超薄聚氧化乙烯基固态电解质薄膜的固态超级电容器的电化学性能图;Fig. 3 is the electrochemical performance diagram of the solid-state supercapacitor based on the ultrathin polyoxyethylene solid-state electrolyte film;

图4为不同厚度的超薄聚氧化乙烯基固态电解质薄膜的台阶仪扫描图;Fig. 4 is the step meter scanning diagram of ultra-thin polyoxyethylene solid electrolyte films of different thicknesses;

图5为不同聚氧化乙烯基固态电解质薄膜的拉伸性能图。Figure 5 is a graph showing the tensile properties of different polyethylene oxide-based solid electrolyte films.

附图标记说明:聚合物支撑基底1、交联修饰的聚氧化乙烯基固态电解质基质2。Description of reference numerals: polymer support substrate 1 , cross-linked modified polyoxyethylene solid electrolyte matrix 2 .

具体实施方式Detailed ways

下面结合实施例对本发明做进一步描述。下述实施例的说明只是用于帮助理解本发明。应当指出,对于本技术领域的普通人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干修饰,这些改进和修饰也落入本发明权利要求的保护范围内。The present invention will be further described below in conjunction with the embodiments. The following examples are illustrative only to aid in the understanding of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, the present invention can also be modified several times, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

实施例1Example 1

如图1所示,一种超薄聚氧化乙烯基固态电解质薄膜,包括:聚合物支撑基底1和交联修饰的聚氧化乙烯基固态电解质基质2,聚合物支撑基底1位于两层交联修饰的聚氧化乙烯基固态电解质基质2之间;聚合物支撑基底1为聚合物薄膜,聚氧化乙烯基固态电解质基质的交联修饰方式为氢键交联。As shown in Figure 1, an ultra-thin polyoxyethylene solid electrolyte film includes: a polymer supporting substrate 1 and a cross-linked modified polyoxyethylene solid electrolyte substrate 2, wherein the polymer supporting substrate 1 is located on two layers of cross-linked modified between the polyoxyethylene solid electrolyte substrates 2; the polymer supporting substrate 1 is a polymer film, and the crosslinking modification mode of the polyoxyethylene solid electrolyte substrate is hydrogen bond crosslinking.

聚合物支撑基底1厚度为5~10μm,聚合物支撑基底1材质为聚四氟乙烯、聚偏氟乙烯和聚酰亚胺中的至少一种。超薄聚氧化乙烯基固态电解质薄膜的整体厚度为5~30μm。The thickness of the polymer support base 1 is 5-10 μm, and the material of the polymer support base 1 is at least one of polytetrafluoroethylene, polyvinylidene fluoride and polyimide. The overall thickness of the ultra-thin polyethylene oxide-based solid electrolyte film is 5-30 μm.

交联修饰的聚氧化乙烯基固态电解质基质2为聚氧化乙烯和电解质盐络合形成的固态电解质基质。聚氧化乙烯基固态电解质基质中交联剂氢键供体与聚氧化乙烯氢键受体的摩尔比为1:1~1:10。The cross-linked modified polyethylene oxide solid electrolyte matrix 2 is a solid electrolyte matrix formed by the complexation of polyethylene oxide and an electrolyte salt. The molar ratio of the hydrogen bond donor of the crosslinking agent to the hydrogen bond acceptor of the polyethylene oxide in the polyoxyethylene solid electrolyte matrix is 1:1-1:10.

实施例2Example 2

超薄聚氧化乙烯基固态电解质薄膜制备及其固态超级电容器性能测试,具体步骤如下:Preparation of ultra-thin polyethylene oxide solid electrolyte film and its performance test of solid state supercapacitor, the specific steps are as follows:

(1)将聚氧化乙烯和双三氟甲磺酰亚胺锂按照锂氧比为1:8称取一定重量,溶于一定体积的乙腈溶剂中,磁力搅拌24h直至完全溶解;(1) take a certain weight of polyethylene oxide and lithium bis-trifluoromethanesulfonimide according to the lithium-oxygen ratio of 1:8, dissolve in a certain volume of acetonitrile solvent, and magnetically stir for 24h until completely dissolved;

(2)按照尿素与聚氧化乙烯摩尔比为1/10,将尿素添加到上述溶液中,磁力搅拌12h直至完全溶解,得到分散液;(2) be 1/10 according to urea and polyoxyethylene mol ratio, add urea to above-mentioned solution, magnetic stirring 12h until completely dissolve, obtain dispersion liquid;

(3)取厚度10μm的聚四氟乙烯(PTFE)薄膜作为支撑基底,在PTFE薄膜两侧分别滴一定体积的步骤2所得分散液;(3) Take a polytetrafluoroethylene (PTFE) film with a thickness of 10 μm as a support substrate, and drop a certain volume of the dispersion obtained in step 2 on both sides of the PTFE film respectively;

(4)采用厚度为100μm的涂布器,对步骤3所滴的分散液进行涂布,对涂布后样品自然晾干;(4) Using a coater with a thickness of 100 μm, coat the dispersion liquid dropped in step 3, and dry the coated sample naturally;

(5)对步骤(4)所得的样品,在3个从大到小的辊压间距下,依次辊压三次,获得超薄聚氧化乙烯基固态电解质薄膜;(5) for the sample obtained in step (4), under 3 rolling spacings from large to small, rolling three times in turn to obtain an ultra-thin polyoxyethylene solid electrolyte film;

采用Bruker Dektak XT-A台阶仪对本实施例步骤5所得厚度为5.5μm的样品进行扫描,得到如图2所示的超薄聚氧化乙烯基固态电解质薄膜的台阶仪扫描图。The Bruker Dektak XT-A step meter was used to scan the sample with a thickness of 5.5 μm obtained in step 5 of this example, and the step meter scan diagram of the ultra-thin polyethylene oxide-based solid electrolyte film as shown in FIG. 2 was obtained.

采用活性炭作为电极,按照0.1mA/mg的电流密度,0~2.5V的电压范围,在50℃下进行充放电循环测试,测试结果如图3所示:经50次循环后,容量保持率可达94%,并且充放电效率保持在90%。Using activated carbon as the electrode, according to the current density of 0.1mA/mg and the voltage range of 0-2.5V, the charge-discharge cycle test was carried out at 50 °C. The test results are shown in Figure 3: after 50 cycles, the capacity retention rate can be up to 94%, and the charge-discharge efficiency remains at 90%.

实施例3Example 3

不同厚度的超薄聚氧化乙烯基固态电解质薄膜,制备过程如下:The preparation process of ultrathin polyoxyethylene solid electrolyte films with different thicknesses is as follows:

(1)将聚氧化乙烯和双三氟甲磺酰亚胺锂按照锂氧比为1:15称取一定重量,溶于一定体积的乙腈溶剂中,磁力搅拌24h直至完全溶解;(1) take a certain weight of polyethylene oxide and lithium bis-trifluoromethanesulfonimide according to the lithium-oxygen ratio of 1:15, dissolve in a certain volume of acetonitrile solvent, and magnetically stir for 24h until completely dissolved;

(2)按照尿素与聚氧化乙烯摩尔比为1/20,称取尿素到上述溶液中,磁力搅拌12h直至完全溶解;(2) be 1/20 according to urea and polyoxyethylene mol ratio, take urea into above-mentioned solution, magnetic stirring 12h until completely dissolved;

(3)取厚度10μm的聚四氟乙烯(PTFE)薄膜作为支撑基底,在PTFE薄膜两侧分别滴一定体积的步骤2制得的分散液;(3) take a polytetrafluoroethylene (PTFE) film with a thickness of 10 μm as a support substrate, and drop a certain volume of the dispersion liquid obtained in step 2 on both sides of the PTFE film;

(4)采用厚度为100μm的涂布器,对步骤3所滴的分散液进行涂布,对涂布后样品自然晾干;(4) Using a coater with a thickness of 100 μm, coat the dispersion liquid dropped in step 3, and dry the coated sample naturally;

(5)对步骤4中的样品,分别在辊压间距为18-16-11-11、18-16-16-16、18-18-18-18下辊压四次,获得三个不同厚度的样品,依次辊压三次,采用的设备为Bruker DektakXT-A台阶仪测试样品厚度。(5) For the sample in step 4, roll four times at rolling intervals of 18-16-11-11, 18-16-16-16, and 18-18-18-18, respectively, to obtain three different thicknesses The samples were rolled three times in turn, and the Bruker DektakXT-A step tester was used to measure the thickness of the samples.

图4为不同厚度的超薄聚氧化乙烯基固态电解质薄膜的台阶仪扫描图,所测样品厚度分别为5.6μm、16.5μm、25.6μm。Figure 4 is a step meter scanning diagram of ultra-thin polyoxyethylene solid electrolyte films with different thicknesses. The measured sample thicknesses are 5.6 μm, 16.5 μm, and 25.6 μm, respectively.

实施例4Example 4

对比聚氧化乙烯基固态电解质拉伸性能,制备过程如下:To compare the tensile properties of polyoxyethylene solid electrolytes, the preparation process is as follows:

(1)将聚氧化乙烯和双三氟甲磺酰亚胺锂按照锂氧比为1:15称取一定重量,溶于一定体积的乙腈溶剂中,磁力搅拌24h直至完全溶解。重复步骤,制备两份溶液;(1) A certain weight of polyethylene oxide and lithium bis-trifluoromethanesulfonimide was weighed according to the lithium-oxygen ratio of 1:15, dissolved in a certain volume of acetonitrile solvent, and magnetically stirred for 24 hours until completely dissolved. Repeat steps to prepare two solutions;

(2)按照尿素与聚氧化乙烯摩尔比为1/10,称取尿素到溶液中,磁力搅拌12h直至完全溶解,编号溶液1。未添加尿素的溶液,编号为溶液2。(2) According to the molar ratio of urea and polyethylene oxide being 1/10, weigh urea into the solution, stir magnetically for 12h until completely dissolved, and number solution 1. Solution without urea added, numbered solution 2.

(3)分别添加15ml溶液1和溶液2于PTFE方盒中,自然晾干,获得薄膜1(含有尿素)和薄膜2(不含尿素);(3) respectively add 15ml solution 1 and solution 2 in the PTFE square box, air dry naturally, obtain film 1 (containing urea) and film 2 (does not contain urea);

(4)将薄膜1/2裁剪为1*2cm的矩形形状,对比薄膜1和薄膜2拉伸性能。(4) Cut 1/2 of the film into a rectangular shape of 1*2 cm, and compare the tensile properties of film 1 and film 2.

图5为不同聚氧化乙烯基固态电解质薄膜的拉伸性能。其中薄膜1的最大力伸长率为60%,而薄膜2仅为19%,薄膜1的拉伸性能优于薄膜2。Figure 5 shows the tensile properties of different polyoxyethylene solid electrolyte films. The maximum force elongation of film 1 is 60%, while that of film 2 is only 19%. The tensile property of film 1 is better than that of film 2.

Claims (10)

1.一种超薄聚氧化乙烯基固态电解质薄膜,其特征在于,包括:聚合物支撑基底(1)和交联修饰的聚氧化乙烯基固态电解质基质(2),聚合物支撑基底(1)位于两层交联修饰的聚氧化乙烯基固态电解质基质(2)之间;聚合物支撑基底(1)为聚合物薄膜,聚氧化乙烯基固态电解质基质的交联修饰方式为氢键交联。1. an ultra-thin polyoxyethylene group solid electrolyte film, is characterized in that, comprises: polymer support base (1) and the polyoxyethylene group solid electrolyte matrix (2) of crosslinking modification, polymer support base (1) The polymer supporting substrate (1) is a polymer film, and the crosslinking modification mode of the polyoxyethylene solid electrolyte matrix is hydrogen bond crosslinking. 2.根据权利要求1所述超薄聚氧化乙烯基固态电解质薄膜,其特征在于:聚合物支撑基底(1)为绝缘多孔材料,厚度为5~10μm,聚氧化乙烯基固态电解质基质2的厚度为5~15μm。2. The ultra-thin polyoxyethylene solid electrolyte film according to claim 1, wherein the polymer support substrate (1) is an insulating porous material with a thickness of 5 to 10 μm, and the thickness of the polyoxyethylene solid electrolyte matrix 2 5 to 15 μm. 3.根据权利要求2所述超薄聚氧化乙烯基固态电解质薄膜,其特征在于:聚合物支撑基底(1)材质为聚四氟乙烯、聚偏氟乙烯和聚酰亚胺中的至少一种。3. The ultra-thin polyoxyethylene solid electrolyte film according to claim 2, wherein the polymer support substrate (1) is made of at least one of polytetrafluoroethylene, polyvinylidene fluoride and polyimide . 4.根据权利要求1所述超薄聚氧化乙烯基固态电解质薄膜,其特征在于:超薄聚氧化乙烯基固态电解质薄膜的整体厚度为5~30μm。4 . The ultra-thin polyethylene oxide-based solid electrolyte film according to claim 1 , wherein the overall thickness of the ultra-thin polyethylene oxide-based solid electrolyte film is 5-30 μm. 5 . 5.根据权利要求1所述超薄聚氧化乙烯基固态电解质薄膜,其特征在于:交联修饰的聚氧化乙烯基固态电解质基质(2)为聚氧化乙烯和电解质盐络合形成的固态电解质基质。5. ultrathin polyoxyethylene solid electrolyte film according to claim 1 is characterized in that: the polyoxyethylene solid electrolyte matrix (2) of cross-linking modification is the solid electrolyte matrix formed by polyoxyethylene and electrolyte salt complexation . 6.根据权利要求1所述超薄聚氧化乙烯基固态电解质薄膜,其特征在于:聚氧化乙烯基固态电解质基质中交联剂氢键供体与聚氧化乙烯氢键受体的摩尔比为1:1~1:10。6. The ultrathin polyoxyethylene solid electrolyte film according to claim 1 is characterized in that: in the polyoxyethylene solid electrolyte matrix, the mol ratio of the crosslinking agent hydrogen bond donor and the polyoxyethylene hydrogen bond acceptor is 1 : 1 to 1:10. 7.一种如权利要求1至6任一项所述超薄聚氧化乙烯基固态电解质薄膜的制备方法,其特征在于,包括以下步骤:7. the preparation method of the ultra-thin polyoxyethylene-based solid electrolyte film as described in any one of claim 1 to 6, is characterized in that, comprises the following steps: 步骤1、将聚氧化乙烯和电解质盐按照设定摩尔比分散到乙腈中,搅拌至完全溶解;Step 1. Disperse polyethylene oxide and electrolyte salt into acetonitrile according to the set molar ratio, and stir until completely dissolved; 步骤2、将交联剂和聚氧化乙烯按照设定氢键受体的摩尔比添加到步骤1所得溶液中,搅拌至完全分散,得到分散液;Step 2, adding the crosslinking agent and polyethylene oxide to the solution obtained in step 1 according to the molar ratio of the set hydrogen bond acceptor, and stirring until completely dispersed to obtain a dispersion; 步骤3、将步骤2所得分散液分别滴于聚合物支撑基底两侧,将分散液涂布均匀,烘干去除溶剂,在聚合物支撑基底两侧得到薄膜;Step 3, drop the dispersion obtained in step 2 on both sides of the polymer support substrate respectively, coat the dispersion evenly, dry to remove the solvent, and obtain a film on both sides of the polymer support substrate; 步骤4、将步骤3得到的薄膜-聚合物支撑基底-薄膜结构置于辊压机中,在从大到小的辊压间隙下多次辊压,获得厚度均匀的超薄聚氧化乙烯基固态电解质薄膜;符号-表示复合连接。Step 4. Place the film-polymer support substrate-film structure obtained in step 3 in a roller press, and roll multiple times under the rolling gap from large to small to obtain an ultra-thin polyoxyethylene solid state with uniform thickness. Electrolyte membrane; symbol - indicates a composite connection. 8.根据权利要求7所述超薄聚氧化乙烯基固态电解质薄膜的制备方法,其特征在于:步骤2中交联剂提供至少两个氢键供体,氢键供体同时与多个聚氧化乙烯链发生氢键交联;具体氢键交联方式为:交联剂提供的氢键供体与聚氧化乙烯中醚氧形成氢键,形成网络化结构;交联剂包括尿素、硫脲和三羟甲基酚。8. according to the preparation method of the described ultrathin polyoxyethylene solid electrolyte film of claim 7, it is characterized in that: in step 2, the crosslinking agent provides at least two hydrogen bond donors, and the hydrogen bond donor is simultaneously with a plurality of polyoxyethylene The ethylene chain undergoes hydrogen bond crosslinking; the specific hydrogen bond crosslinking method is: the hydrogen bond donor provided by the crosslinking agent forms a hydrogen bond with the ether oxygen in the polyethylene oxide to form a network structure; the crosslinking agent includes urea, thiourea and Trimethylolphenol. 9.根据权利要求7所述超薄聚氧化乙烯基固态电解质薄膜的制备方法,其特征在于:步骤1中聚氧化乙烯和电解质盐的摩尔比为1:8~1:20;步骤2中交联剂和聚氧化乙烯中氢键受体的摩尔比为1:1~1:10;步骤3中将分散液涂布均匀后,在60℃下烘干12h去除溶剂。9 . The method for preparing an ultra-thin polyethylene oxide solid electrolyte film according to claim 7 , wherein the molar ratio of polyethylene oxide and electrolyte salt in step 1 is 1:8 to 1:20; The molar ratio of the linking agent and the hydrogen bond acceptor in the polyethylene oxide is 1:1 to 1:10; in step 3, after the dispersion liquid is uniformly coated, the solvent is removed by drying at 60° C. for 12 hours. 10.根据权利要求7所述超薄聚氧化乙烯基固态电解质薄膜的制备方法,其特征在于:步骤3中将分散液涂布在聚合物支撑基底两侧时的涂布高度为100~500μm。10 . The method for preparing an ultra-thin polyethylene oxide solid electrolyte film according to claim 7 , wherein in step 3, the coating height when the dispersion is coated on both sides of the polymer support substrate is 100-500 μm. 11 .
CN202210372914.5A 2022-04-08 2022-04-08 Ultrathin polyoxyethylene-based solid electrolyte film and preparation method thereof Active CN114613615B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210372914.5A CN114613615B (en) 2022-04-08 2022-04-08 Ultrathin polyoxyethylene-based solid electrolyte film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210372914.5A CN114613615B (en) 2022-04-08 2022-04-08 Ultrathin polyoxyethylene-based solid electrolyte film and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114613615A true CN114613615A (en) 2022-06-10
CN114613615B CN114613615B (en) 2024-12-17

Family

ID=81868543

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210372914.5A Active CN114613615B (en) 2022-04-08 2022-04-08 Ultrathin polyoxyethylene-based solid electrolyte film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114613615B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116130881A (en) * 2022-11-17 2023-05-16 惠州锂威新能源科技有限公司 Gel state battery diaphragm, preparation method thereof and lithium sulfur battery

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1267683A (en) * 1999-03-17 2000-09-27 小山昇 Polymer electrolyte
JP2000268866A (en) * 1999-03-18 2000-09-29 Fujitsu Ltd Solid electrolyte and battery using it
CN103950239A (en) * 2014-04-24 2014-07-30 合肥国轩高科动力能源股份公司 Multifunctional composite film for chemical power source
CN104103791A (en) * 2013-04-08 2014-10-15 中国科学院金属研究所 Composite diaphragm for battery and preparation method thereof
CN107768729A (en) * 2017-10-26 2018-03-06 电子科技大学 A kind of implantation polymer particles solid electrolyte in situ and preparation method thereof
CN110233064A (en) * 2019-06-28 2019-09-13 西安交通大学 A kind of big depth-to-width ratio, the manufacturing method of high load miniature ultracapacitor
CN111313089A (en) * 2020-01-03 2020-06-19 武汉理工大学 A kind of preparation method of ion conductor/polyethylene oxide composite solid electrolyte based on ultraviolet cross-linking
CN111341568A (en) * 2020-03-17 2020-06-26 浙江浙能技术研究院有限公司 Preparation method of graphene mixed film
CN111403183A (en) * 2020-03-26 2020-07-10 浙江浙能技术研究院有限公司 Electrode-diaphragm structure composed of graphene film-insulating filter membrane
CN111584933A (en) * 2020-05-19 2020-08-25 湘潭大学 A kind of solid electrolyte and its preparation method and battery
CN111584932A (en) * 2020-05-15 2020-08-25 江苏大学 A kind of layered composite solid electrolyte film and preparation method thereof
CN112952192A (en) * 2021-03-12 2021-06-11 上海交通大学 Preparation method and application of polyamino azulene-doped organic polymer electrolyte film
CN113937367A (en) * 2021-10-12 2022-01-14 中国科学院苏州纳米技术与纳米仿生研究所 A kind of polymer matrix composite solid electrolyte and its preparation method and application

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1267683A (en) * 1999-03-17 2000-09-27 小山昇 Polymer electrolyte
JP2000268866A (en) * 1999-03-18 2000-09-29 Fujitsu Ltd Solid electrolyte and battery using it
CN104103791A (en) * 2013-04-08 2014-10-15 中国科学院金属研究所 Composite diaphragm for battery and preparation method thereof
CN103950239A (en) * 2014-04-24 2014-07-30 合肥国轩高科动力能源股份公司 Multifunctional composite film for chemical power source
CN107768729A (en) * 2017-10-26 2018-03-06 电子科技大学 A kind of implantation polymer particles solid electrolyte in situ and preparation method thereof
CN110233064A (en) * 2019-06-28 2019-09-13 西安交通大学 A kind of big depth-to-width ratio, the manufacturing method of high load miniature ultracapacitor
CN111313089A (en) * 2020-01-03 2020-06-19 武汉理工大学 A kind of preparation method of ion conductor/polyethylene oxide composite solid electrolyte based on ultraviolet cross-linking
CN111341568A (en) * 2020-03-17 2020-06-26 浙江浙能技术研究院有限公司 Preparation method of graphene mixed film
CN111403183A (en) * 2020-03-26 2020-07-10 浙江浙能技术研究院有限公司 Electrode-diaphragm structure composed of graphene film-insulating filter membrane
CN111584932A (en) * 2020-05-15 2020-08-25 江苏大学 A kind of layered composite solid electrolyte film and preparation method thereof
CN111584933A (en) * 2020-05-19 2020-08-25 湘潭大学 A kind of solid electrolyte and its preparation method and battery
CN112952192A (en) * 2021-03-12 2021-06-11 上海交通大学 Preparation method and application of polyamino azulene-doped organic polymer electrolyte film
CN113937367A (en) * 2021-10-12 2022-01-14 中国科学院苏州纳米技术与纳米仿生研究所 A kind of polymer matrix composite solid electrolyte and its preparation method and application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116130881A (en) * 2022-11-17 2023-05-16 惠州锂威新能源科技有限公司 Gel state battery diaphragm, preparation method thereof and lithium sulfur battery

Also Published As

Publication number Publication date
CN114613615B (en) 2024-12-17

Similar Documents

Publication Publication Date Title
Ghazi et al. MoS2/celgard separator as efficient polysulfide barrier for long‐life lithium–sulfur batteries
CN108878964B (en) Composite gel polymer electrolyte, preparation method and application thereof in lithium air battery
Raja et al. A chitosan/poly (ethylene glycol)-ran-poly (propylene glycol) blend as an eco-benign separator and binder for quasi-solid-state supercapacitor applications
Gou et al. A renewable gel polymer electrolyte based on the different sized carboxylated cellulose with satisfactory comprehensive performance for rechargeable lithium ion battery
CN113725421B (en) Preparation method and application of covalent organic framework material modified zinc cathode
CN107959049A (en) Preparation method, gel electrolyte and the lithium ion battery of gel electrolyte
CN107069079A (en) A kind of solid state electrolyte and its preparation and application
CN103474723A (en) Lithium-air battery and preparation method thereof
CN111725468A (en) A kind of silica inorganic nanoparticles reinforced polyolefin separator and its application
CN114400374B (en) Polymer electrolyte, all-solid-state high-voltage lithium metal battery and preparation method thereof
Xiao et al. An integrated separator/anode assembly based on electrospinning technique for advanced lithium-ion batteries
CN110993375A (en) Method for preparing compact-structure RGO/MXene-sulfuric acid supercapacitor flexible electrode in one step and application thereof
CN114171788A (en) Sandwich type solid composite electrolyte membrane and preparation method and application thereof
CN115360344A (en) Composite positive electrode material for sodium ion battery and preparation method thereof
CN111825880A (en) A high frequency response porous PEDOT:PSS thin film material and its preparation method and application
Xu et al. All solid supercapacitors based on an anion conducting polymer electrolyte
CN118763293A (en) A positive electrode-solid electrolyte integrated material and its preparation method and application
CN102842433B (en) Electrode material for super capacitor and preparation method and the ultracapacitor made by it
Xu et al. Structural engineering for high energy and voltage output supercapacitors
CN114613615A (en) Ultrathin polyoxyethylene-based solid electrolyte film and preparation method thereof
Zhang et al. Effect of UV light polymerization time on the properties of plastic crystal composite polyacrylate polymer electrolyte for all solid‐state lithium‐ion batteries
Nie et al. Highly Stable Supercapacitors Enabled by a New Conducting Polymer Complex PEDOT: CF3SO2 (x) PSS (1‐x)
Cui et al. Quasi‐Solid‐State Composite Electrolytes with Multifunctional 2D Molecular Brush Fillers for Long‐Cycling Lithium Metal Batteries
CN107359055A (en) A kind of breathable symmetric form flexibility all-solid-state supercapacitor and preparation method thereof
Xiang et al. A Novel EDOT/F Co‐doped PMIA Nanofiber Membrane as Separator for High‐Performance Lithium‐Sulfur Battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant