CN114613615A - Ultrathin polyoxyethylene-based solid electrolyte film and preparation method thereof - Google Patents
Ultrathin polyoxyethylene-based solid electrolyte film and preparation method thereof Download PDFInfo
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Abstract
Description
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
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;
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;
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
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。
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
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
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:
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
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
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
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
(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
(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
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
(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
(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)
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
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